12th Organic Chemistry (DPP)

Std.
12 Topic : Organic Chemistry (DPP)

CHEMISTRY
DAILY PRACTICE PROBLEMS
Std. 11th &12th Draw Resonance hybrid of the following compounds DPP 1
1
2
CHEMISTRY
Std. 11th &12th Compare relative stability of following resonating structures DPP 2
3
4
CHEMISTRY
Std. 11th &12th Compare relative stability of following resonating structures DPP 3
5
6
CHEMISTRY
Std. 11th &12th Identify no. of  -hydrogen in the following compounds DPP 4
7
8
CHEMISTRY
Std. 11th &12th Identify no. of  -hydrogen in the following compounds DPP 5
9
10
CHEMISTRY
Std. 11th &12th Give the relative Stability of the following compound DPP 6
11
CHEMISTRY
12
CHEMISTRY
13
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14
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15
CHEMISTRY
Std. 11th &12th Hyperconjugation DPP 11
16
17
18
19
20
CHEMISTRY
Std. 11th &12th Stability of Intermediate DPP 12
21
22
23
24
25
26
CHEMISTRY
Std. 11th &12th Identify the Nature of compound DPP 13
27
CHEMISTRY
28
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29
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30
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31
CHEMISTRY
32
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33
CHEMISTRY
Std. 11th &12th Compare Acidic Strength DPP 20
34
35
CHEMISTRY
36
37
CHEMISTRY
38
39
CHEMISTRY
Std. 11th &12th Compare which is more basic in nature DPP 23
40
CHEMISTRY
Std. 11th &12th Compare which is more basic in nature DPP 24
41
42
CHEMISTRY
Std. 11th &12th Which Nitrogen is most basic DPP 25
43
ANSWER KEY GOC
Answers of DPP No. – 1

+
+
1. – – OH 2. – 3.
+
–
O
–
– O
O
+ –
– O –
4. 5. 6. + 7. NH
+ + +
+
–
O
– + – +
O – CH — CH — NH2 CH — CH — NH2
– – –
8. 9. – or
– –
– –
O H O H
O O
O –
+ –
10. H2N O 11. 12. H
– – –
O
– –
O O
+ +
CH2 + CH2
+ +
13. 14. + or 15. Me — S — CH 2
+ +
– –
O O
+ O –
Me — N
– + + –
16. O 17. 18. H2N — C — N: 19. N+
–
O O –
–
Me
+ – – + + –
20. O — C — O or O — C — O 21. O N:
–
+ +
H2N NH2 O –
22. C 23. 24.
+ + + + +
NH OH
– +
44
– – O
O O –
–
25. 26. + 27. – 28.
– –
–
– –
O O
O –
– –
29. – or 30. –
C—O
–
– O
– –
O O
– – + +
CH2 CH2 NH2 NH2
– – – –
31. – or 32. – or
– –
N+ N +
– –
O O – O O –
1. a>b 2. b>a 3. b>a 4. b>a 5. a>b>c
6. a>b 7. a>b 8. ------ 9. a=b=c 10. a=b
11. b>a 12. b>a 13. a>c>b 14. a>b>c 15. c>a>b
16. b>a 17. a>b 18. b>a 19. a>b 20. b>c>a
1. a>b>c 2. a=b 3. a>b 4. a=b 5. b>a
6. a>b 7. b>a 8. b>a 9. b>a 10. a=b
11. a>b 12. b>c>a 13. b>a 14. b>a 15. a>b
16. b>a 17. b>a 18. a>b=c 19. a>b 20. a>b
1. 4 2. 5 3. 6 4. 8 5. 2
6. 8 7. 6 8. 6 9. 6 10. 10
11. 5 12. 3 13. 3 14. 2 15. 5
16. 5 17. 2 18. 12 19. 4 20. 4
1. 5 2. 8 3. 5 4. 3 5. 2
6. 1 7. 0 8. 4 9. 2 10. 7
11. 1 12. 6 13. 3 14. 3 15. 4
16. 7 17. 6 18. 4 19. 6 20. 0
Answers of DPP No. –6
1. i > ii > iii > iv > v 2. iii > i > ii > iv 3. i > ii > iv > iii
4. i > iii > iv > ii 5. i > iv > ii > iii 6. i > iii > ii > iv
7. iv > ii > iii > i
45
1. i > ii > iii > iv > v > vi > vii 2. i > ii > iii > iv 3. i > ii > iii > iv
4. i > ii > iii > iv 5. i > ii > iii > iv 6. ii > i > iv > iii
1. i > iii > ii 2. iii > ii > iv > i 3. iii > ii > iv > i
4. iii > ii > iv > i 5. i > ii > iv > iii 6. i > ii > iv > iii
7. ii > iii > i
1. ii > i > iii 2. i > ii > iii 3. ii > i > iii
4. i > ii > iii 5. ii > i > iii 6. i > ii
7. iv > iii > ii > I 8. ii > i
Answers of DPP No. –10
1. ii > I 2. i > ii 3. i > ii
4. iii > i > ii 5. i > ii 6. ii > i
7. i > ii 8. i > ii 9. i > ii
10. i > ii Q.2 A
1. D 2. A 3. D 4. B 5. B
6. C 7. D 8. A 9. A 10. A
11. A 12. C 13. D 14. B 15. A
16. D 17. B 18. C 19. A 20. D
21. C 22. A 23. A 24. C 25. C
26. C 27. D 28. D 29. D 30. B
1. C 2. C 3. A 4. C 5. B
6. C 7. A 8. A 9. D 10. A
11. A 12. B 13. C 14. A 15. A
16. B 17. C 18. D 19. C 20. C
21. A 22. A 23. C 24. A 25. C
26. A 27. A 28. B 29. B 30. A
Aromatic : Aro, Antiaromatic : A.A. Non-aromatic : N.A.
1. NA 2. AA 3. Aro 4. Aro 5. Aro
6. NA 7. NA 8. NA 9. Aro 10. AA
11. AA 12. Aro 13. Aro
1. AA 2. Aro 3. Aro 4. Aro 5. NA
6. Aro 7. NA 8. NA 9. Aro 10. NA
11. Aro
1. Aro 2. Aro 3. Aro 4. Aro 5. Aro
46
6. NA 7. Aro 8. Aro 9. Aro
1. Aro 2. AA 3. Aro 4. Aro 5. Aro
6. NA 7. Aro 8. Aro 9. Aro
1. Aro 2. Aro 3. Aro 4. Aro 5. Aro
6. Aro 7. Aro 8. AA 9. Aro
1. Aro 2. NA 3. Aro 4. Aro 5. Aro
6. AA 7. AA 8. Aro 9. Aro
1. Aro 2. Aro 3. NA 4. Aro
H *
– *
* * H
2. (A) (B) (C) (D)
H
3. 6; aromatic 6; aromatic 6; neither 10; aromatic
Acidic strength is directly proportional to Ka and inversely proportional to pKa. so pKa is just inverse
of Ka. Ka is given.
1. a 2. b 3. b 4. a 5. a
6. a 7. a 8. a 9. b 10. a
11. b 12. a 13. a 14. b 15. a
16. b

Acidic strength is directly proportional to Ka and inversely proportional to pKa. so pKa is just inverse
of Ka. Ka is given.
1. b 2. b 3. a 4. a 5. b
6. a 7. b 8. b 9. a 10. a
11. a 12. b 13. b 14. a 15. b
16. b 17. a 18. a 19. a 20. a

1. 1>4>3>2
2. (a) Carboxy H is more acidic than hydroxyl or thioxy hydroxyl, between —OH and —SH, latter H is
more acidic thus the order of acid strength is: c < b < a
(b) x > y > z
3. a>c>b>d
47
–
O
–
O O
Less stable anion
I Me I Me
I Me
4. 
N=O
– No –R effect
N=O N=O O
O O Out of plane
5. C 6. B 7. C 8. C 9. C 10. A
Basic strength is directly proportional to Ka and inversely proportional to pKb. so pKb is just inverse
of Kb. Kb is given.
1. b 2. a 3. a 4. b 5. b
6. b 7. a
Basic strength is directly proportional to Ka and inversely proportional to pKb. so pKb is just inverse
of Kb. Kb is given.
1. b 2. b 3. a 4. a 5. b
6. a 7. a 8. a 9. b 10. b
11. a 12. b 13. b 14. b 15. b
1. (i) a > b (ii) b > a > c (iii) b > a (iv) b > a (v) a > b (vi) a > b = c
(vii) b > a (viii) a > b
2. II > I
48
CHEMISTRY
Std. 11th &12th DEGREE OF THE ELEMENT DPP 1
Single Choice Questions :
1. Which of following is 3° (tertiary alcohol)
OH OH OH
(A) (B) (C) (D) All
2. Which of following is 1° amine ?
NH2 CH3
(A) (B) CH3 – C – NH2 (C) CH3 – NH2 (D) All
CH3
3. Which of following is 3° amine ?
CH3
(A) CH – N (B) CH3 – NH – Et (C) CH3 – NH – CH3 (D) CH3 – NH2
3
CH3
4. and
Number of secondary carbon atoms present in the above compounds are respectively:
(A) 6, 4, 5 (B) 4, 5, 6 (C) 5, 4, 6 (D) 6, 2, 1
5. Number of 1°, 2° and 3° hydrogen in isooctane is:

(A) 9,8,1 (B) 12,5,1 (C) 15,2,1 (D) None of these
Multiple Choice Question :
6. Which of the following compound contain all 1°, 2°, & 3° amine
N NH2
NH2
(A) H2.N NH (B)
N
H
NH2
N
N N
(C) (D)
N N
49
7. Which of the following compound contain only 1 type of carbon atom
(A) (B) (C) (D)
8. Which of the following compound contain only 2 types of carbon atom
N N
(A) (B) N N (C) (D)
N N
9. Which of the following is a 2° amine.
NH2
H
N
(A) C  C  C  C (B) (C) (D)
| N
NH 2
H
10. Classify the following alcohols as primary, secondary, or tertiary:

(a) (CH3)3CCH2OH (b) CH3CH(OH)CH(CH3)2
(c) (CH3)2C(OH)CH2CH3 (d)
(e)
11. Classify the following amines as primary, secondary, or tertiary:

(a) CH3NHCH(CH3)2 (b) CH3CH2CH(CH3)CH2NH2
(c) (CH3CH2)3N (d) (C6H5)2CHCH2NHCH3
(e) (f)
50
CHEMISTRY
Std. 11th &12th DOUBLE BOND EQUIVALENT (D.B.E) DPP 2
1. Find - D.B.E. of the following
(Write your answer in box)
(1) C4 H10 (2) C4H8
(3) C4H6 (4) C5H12O
(5) C5H10O (6) C5H8O
(7) C6H12 (8) C4H8Cl2
(9) C4H8Br2 (10) C4H10O
(11) C10H20 (12) CNH5
(13) C3H6O (14)
O
(15) (16)
(17) (18)
(19) (20)
CH2 CH2
O
(21) (22)
CH2 CH2 O
O
O
C–O–H
(23) (24) CH –C–O–H
3
(25) CH3 – NH2 (26) C2H3N
51
2. Match the column :
Column I Column II
(Compound) (Double bond equivalent)
(A) (P) 4
H
CH3
C—N S
O
O N
COOH
(penicillin)
(B) (Q) 5
(Hexahelicene)
(C) (R) 7
(Prismane)
O
C OH
(D) C (S) 19
C OH
O
(Ninhydrin)
3. Match the column :

Column I Column II
(Compound) (Double bond equivalent)
(A) (P) 5
(Limonene)
(B) (Q) 4
(Zingiberene)
(C) (R) 3
(Pyrene)
(D) (S) 12
(Cubane)
52
CHEMISTRY
Std. 11th &12th DOUBLE BOND EQUIVALENT (D.B.E) DPP 3
Calculate DBE value -
–
COO
1. 2. 3.
COOH
H OH
4. 5. 6. H OH
COOH
O
||
7. NH 8. 9.
||
O
10. 11. .. 12.

N
H
CN
CH3
H Br
13. 14. 15.
H Br
|| CH3
O
O O
OH
16. 17. 18.
19. 20. 21. C9H16 NOCl

COOH
COOH
53
CHEMISTRY
Std. 11th &12th BASIC ISOMERISM DPP 4
1. How many ether is/are possible for molecular formula C4H10O.
(A) 1 (B) 2 (C) 3 (D) 4
2. How many ketone is/are possible for molecular formula C4H8O
(A) 1 (B) 2 (C) 3 (D) 4
3. How many alcohol is/are possible for Molecular farmula C4H10O (only structural)
(A) 2 (B) 3 (C) 4 (D) 5
O
O–H
4.
O
Number of Functional group in above compound is

(A) 3 (B) 4 (C) 5 (D) 6
5. The functional groups in Cortisone are : HOH2C

(A) Ether, alkene, alcohol CH3 OCH3
O
(B) Alcohol, ketone, alkene, ether
(C) Alcohol, ketone, amine
(D) Ether, amine ketone
O O Cortisone
O
O–H
6. H SH
OH
OH
How many types of functional groups are present in given compound.
(A) 6 (B) 5 (C) 4 (D) 7
CH3 O
7. Present functional group is

O CH3
(A) ketone (B) ester (C) ether (D) alcohol

8. Present functional group is/ are
O O
||
OCCH3
O
(A) ketone (B) ester (C) ether (D) A and B both
54
CHEMISTRY
Std. 11th &12th BASIC ISOMERISM DPP 5
1. Circle the functional group & also find out the degree of unsaturation
O
H
N H
N
O H
(i) (ii) O
N O
Me
OH O
O
O Cl
(iii) H (iv)
H
O O O O
OH O
O
O O HO O
O
N
(v) (vi)
O
NH2
O O O O NH2
2. Which of following is phenol ?

OH OH OH
(A) (B) (C) (D)
OH
NH2 OH
3. OH
O
H
O NH2
(i) Which functional group is not present in above compound ?

(A) Ketone (B) Carboxylic acid (C) Amine (D) Alcohol
(ii) Which functional group is present in above compound ?
(A) Ester (B) 2° amine (C) Alkyne (D) Amide
(iii) Types of functional group is present in above compound
(A) 5 (B) 6 (C) 7 (D) 8
(iv) Degree of unsaturation in above compound is
(A) 5 (B) 6 (C) 7 (D) 8
(v) Above compound is Bicyclo (A) Yes (B) No
(vi) Above compound is spiro (A) Yes (B) No
55
O O
C–NH2
4.
NH2 OH
H O
(A) Ketone (B) Carboxylic acid (C) Amine (D) Alcohol
(A) 5 (B) 6 (C) 7 (D) 8
(A) 5 (B) 6 (C) 7 (D) 8
Me
NH2 c
b
N S
5.
O N
H a– O
d Me O–H
e
(A) Ketone (B) Phenol (C) Amine (D) Alcohol
(A) 5 (B) 6 (C) 7 (D) 8
(A) 5 (B) 6 (C) 7 (D) 8
Observe following compound and answer questions given below.
OH (d)
OH (c)
O
(e)
O
HO
6. O
N N
Me
OH H
(a) (b)
(i) Total number of different types of functional groups in this compound are
(A) 5 (B) 6 (C) 7 (D) 8
56
CHEMISTRY
Std. 11th &12th RELATIONSHIP OF COMPOUNDS - STRUCTURAL ISOMERISM DPP 6
Compounds Relationship
1. &
O
2. &
O
3. &
4. &
Cl Br
5. &
Br Cl
6. CH2 = CH – CH2 OH CH2 = CH–OCH3
O
7. O &
O
||
8. CH2 – CH – CH2OH CH 3– C – OCH 3
O
9. &
10. &
11. &
12. CH3OCH3 & CH3OCH2CH3
57
CHEMISTRY
Std. 11th &12th RELATIONSHIP OF COMPOUNDS - STRUCTURAL ISOMERISM DPP 7
Compounds Relationship
1. &
2. &
O CHO
SH
HS OH
3. &
OH
H CH3
.. .. .. ..
4. &
Et H H H
CH3 Et
OH
OH
5. &
OCH3
6. OCH3 &
CH3 CH2CH3
H Br H Br
7. H Cl & H Cl
CH2CH3 CH3
CH3 Me
8. H Cl & Cl H
Me CH3
Br Br
Cl H
9. &
CH3 H Cl CH3
N
10. | & N
H
58
CHEMISTRY
Std. 11th &12th CHIRAL CENTER DPP 8
Q. Count the total number of Chiral Center.
CH3
O CH
CH3 CH2 CH2 CH2 CH2
1. CH CH2 2. 3. CH2 CH
CH CH C
CH3
O CH3 CH3 H
CH3
CH2 CH2
H2C CH CH
O
CH2 CH2
4. H2C CH OH 5. CH 6. NH2 – CH – COOH
CH2 CH2 CH |
CH2 CH2 CH3
CHO CHO CH3

H OH H OH H Me
7. 8. H OH 9.
H OH H OH H Et
CH2OH CH2OH C2H5
O
O
10. NH 11. 12. Ph – S – CH3
.. 16 O
+
H As C 2H 5 ||
13. CH3 N Ph 14. 15. CH3 — S — Ph
D CH 3 H ||
18 O
16. 17.
HO HO
Cholesterol Estrone
59
CHEMISTRY
Std. 11th &12th MOLECULAR SYMMETRY DPP 9
Q. If there is presence of given symmetry then write () otherwise (×)
Compound P.O.S() C2 C3 COS

(a) CH4
(b)
(c)
(d)
Cl Cl
(e) C=C
H H
Cl H
(f) C=C
H Cl
H
Br
(g) H
Br
CO2H
H OH
(h) HO H
CO2H
60
CHEMISTRY
Std. 11th &12th GEOMETRICAL ISOMERISM DPP 10
Q. How many compounds show geometrical isomerism ?
H3C CH3
(1) CH2 (2) (3) H3C CH3
H3C
Cl
H3C CH2
CH2
(4) (5) (6) H3C
H3C CH3
Cl
H3C CH3 Cl
H3C
(7) (8) (9)
CH2 CH3
Cl
H2C H3C
(10) H3C CH3 (11) (12) CH3
CH3
Br
H3C CH3
(13) (14) H3C CH2 (15)
OH
H3C H2C CH3

CH3
(16) (17) (18)
CH2 CH2
H3C H3C CH3

CH3
(19) (20) (21)
OH CH2 CH3
61
H3C H3C CH3
(22) CH3 (23) (24)
H3C CH3
H3C
(25) (26) CH3 (27)
CH3 CH2
H2C CH2 H3C CH3

H3C
(28) (29) CH3 (30)
H3C CH2
H3C
CH3
H3C CH3
(31) (32)
CH3 CH3
H3C H2C
(33) CH3 (34) CH3
OH Cl
Br Cl H3C Br
(35) (36) CH3 (37)
I Br Cl
HO Br
I
Cl
I
Br
(38) (39) (40)
HO OH
Cl
Cl
CH3
H3C CH3 CH3
(41) (42) CH3 (43)
O OH CH3
CH3
H3C CH2 H3C

CH3 OH
(44) (45) (46)
OH OH
62
CH2
OH
HO H3C
CH3 H3C CH3
(47) (48) (49)
H3C CH3 OH
H2C
H3C CH3 OH
Cl
(50) (51) (52)
OH OH
CH2
O
OH OH
(53) CH3 (54) (55)
H3C
CH3
CH3
(56) (57) Br
O
Cl
CH3
H3C
CH3
H3C H3C
H3C H3C
(58) CH3 (59)

CH3
CH3 CH3
CH3
H3C CH3
OH
OH
OH
CH3
(60) (61) (62)
63
CH3
H3C CH3
CH3
(63) (64) (65)

CH3
CH3
CH3
CH3
(66) (67) (68)

H3C CH3 CH2
CH3
(69) (70) CH3 + O

N
-
O
(71) (72)
N N
N
Br
Br Br
(73) (74) (75)
64
CH3 CH3
(76) OH (77) (78) CH3 (79)

CH3
Br
(80) (81) (82) (
Br
Br Br
83) (84) (85) (86)
Br Br
H3C CH3
Cl
Cl Cl
Cl
CH3
(87) (88) (89) Cl Cl
Cl
H3C
Cl Cl Cl Cl
(90) (91) (92)

Cl
CH3
H3C
CH3
H3C
(93) (94) (95)
CH3
CH3
65
CH3
(96) (97)
OH
(98) (99) (100)
OH
CH3 Cl
NH
CH3
(101) (102) (103)
HN
Cl
NH2
N
NH
+ +
(104) (105) (106) O O
NH NH2 H H
Cl
(107) (108) (109)

O O
Cl
(110)
66
CHEMISTRY
1. Bongkrekic acid is a toxic compound produced by Pseudomonas cocovenenans, and isolated from a mold
that rows on bongkrek, a fermented Indonesian coconut dish. (a) Label each double bond as E, Z or neither
(N).
COOH
-How many total Geometrical Isomers
---------------------------------------------------- COOH OCH3
-How many sites of unsaturation
----------------------------------------------------
Bongkrekic acid
COOH
CH3 CH3 CH3 H

2. C=C=C C=C=C
H l1 H H l2 CH3
(I) (II)
I amd II are not geometrical isomers of each other because

(A) l1 = l2 (B) l1 > l2 (C) l2 > l1 (D) they are geometrical isomers
CH3 l1 CH 3 CH3 l2 H
C=C=C=C C=C=C=C
3. H H H CH3
(I) (II)
I and II are geometrical isomers of each other because

(A) l1 = l2 (B) l1 > l2 (C) l2 > l1 (D) they are geometrical isomers
4. MeCH = CH – CH = C = CH – CH = CH2
Total number of geometrical isomers possible for above compounds are:
(A) 16 (B) 8 (C) 4 (D) 2
5. Which one of the following compounds has (Z) configuration about the C – C double bond?
(A) (B) (C) (D)
67
6. Find total number of Geometrical isomerism of following compounds.
(a) CH3–CH=CH–CH=N–OH (b) (c)
(d) CH3–(CH=CH)3 – Ph (e) (f) CH3–CC–CH=CH–CH3
7. Which of the following compound can show geometrical isomerism.
(A) (B) (C) (D)
8. The geometrical isomerism is shown by
(A) (B) (C) (D)
9. Which of the following double bond will not exhibit geometrical isomerism.
(A) (B) (C) (D) Me–N=N–Me
10. Assign E & Z configuration to following compounds.
(A) (B) (C) (D)
68
CHEMISTRY
Priority will be decided according to (CIP) rules :
(a) Priority will be decided on the basis of Atomic number when isotope is present priority will be assigned on the
basis of atomic mass.
(b) When group has multiple bonds, then all  bonds are break down and hypothetical atoms are attached to
free valencies of group, then priority is assign on the basis of first attached atom.
(c) When real and hypothetical groups are same the real is preffered over pseudo (hypothetical)
(d) When lone pair is present at terminal position of restricted rotation, then it is treated as zero atomic number.
(e) When cyclic is present, it will break and hypothetical atom is attached to free valency and the priority will
assign.
(1) (2)
(3) (4)
O O
HO—CH2 O
O
C=C C=C O
(5) O (6)
NC
O
O
O
HO–C CH2O—Cl HOH2C CN
C=C C=C
(7) (8)
COCl OHC CH2–OH
HOH2C
CH3 CH3
CH2=CH C——C—H
Me
C=C C=C CH3 CH3
(9) (10)
CH2–CH CCH
Me Me
Me
CH C C—H F H
Me C=C
(11) C=C (12)
HO—CH2 C N Cl D
O
H
H CH2–CH2–Br
Cl
(13) (14)
Br CH2–CH2–Cl
O
69
CHEMISTRY
Std. 11th &12th CALCULATION OF GEOMETRICAL ISOMERS DPP 13
Calculation of geometrical isomer :
Case I  If both the ends are different
2n when n is number of stereogenic area or bond which can show G.I.
Case II  If both the ends are same
2n–1 + 2p–1
If n = even ; P = n/2
n 1
If n = odd ; P =
2
Hint Rules for cyclic system :
(i) 3 member to 7 member cyclo alkene exist in only cis form.
(ii) 8 to 11 member can form cis & trans but cis is more stable
(iii) from 12 member trans is more stable.
Q. Calculate total number of only geometrical isomers in following compounds (Theoritical).
(1) (2)
(3) (4)
(5) (6)
Me Me
(7) (8)
H H
H Me
H
(9) (10)
Me
(11) (12)
70
(13) (14)
H Me
(15) (16) Br – CH = C = C = CH – CH = CH – Br
H D
H
(17) (18)
CH3 H
(19) (20) CH3—CH=CH CH=CH—CH3
H CH=C=CH2
CH3
(21) (22)
H
71
CHEMISTRY
Std. 11th &12th RELATIONSHIP OF COMPUNDS DPP 14
Find relationship between given pairs
Identical Enantiomer Diastereomer Constitutional Other

isomer
(1)
(a) (b)
OH OH OH
(2)
OH OH OH
(a) (b) (c)
(3)
CO2H CO2H
(a) (b)
H Me H H
(4)
Me H Me Me
(a) (b)
H H
(5)
(a) (b)
Me Et
H OH HO H
(6) H OH HO H
Et Me
(a) (b)
72
isomer
Cl Cl Cl
Cl
(7)
Br Br Br Br
(a) (b)
(8)
(a) (b)
OH OH
(9)
(a) (b)
(10) OH OH
O O
(a) (b)
73
CHEMISTRY
1. Find relationship between given pairs
isomer
H2C = N CH = NH
O
(1)
O
(a)
H2C = N
CH = NH
O
(b)
O
OH
(2) C
H Me
(a)
Me
C H
OH
O
(b)
COOH H
H Br Br COOH
(3) H CN HO H
OH CN
(a) (b)
O O
(4)
Br Br
(a) (b)
H Br Br Me
(5) H Br
Br H H
(a) (b)
O OH
(6)
(a) (b)
74
isomer
CH3 CH3
H OH HO H
(7) H OH H OH
CH3 CH3
(a) (b)
CH3
H OH
HO H
CH3
(c)
CO2H CO2H
H OH HO H
(8) H OH HO H
CO2H CO2H
(a) (b)
F I Br
H Br H
(9)
I Cl Br Br Cl F
F
H D OH H D
H
(10) F
OH H
HO OH
Br H Br H Br CH3
(11)
H CH3 CH3 CH3 Br H
CH3 CH3
Br H H Br
(12)
H Br Br H
CH3 CH3
Cl Cl Br Cl
Br Br
Br Cl
(13)
CH3 CH3
CH3 CH3
75
CHEMISTRY
1. Find relationship between given pairs

isomer
OH H
H3C CH3
(1)
H OH
H3C CH3
H
H H
H H
(2) H H H H
H CH3
Me
CH3 CH3
H H H H
(3)
H H H CH3
CH3 H
Cl OH
H H Cl
Cl
(4)
OH H Cl H
OH OH
CH3 OH
| |
(5) | C H & | C CH3
HO CH3CH2CH2 H
CH2CH2CH3
CH2Br Cl
| |
(6) | C Cl and | C CH3
CH3 CH3CH2 CH Br
CH2CH3 2
CH2Br H
| |
(7) | C OH and | C CH3
H HO CH Br
CH3 2
Cl CH3
CH3 CH2CH3 & H Cl
(8)
H CH2CH3
(9) OH
OH
(a) (b)
O O
(10)
(a) (b)
76
CHEMISTRY
Std. 11th &12th OPTICAL ISOMERISM DPP 17
S.No Compound Optically Chiral Achiral Optically No. of

active mole. mole. inactive Chiral Center
1.
H CO2H H
2.
HO CO2H OH
3.
OH H CO2H
4.
CO2H H OH
5.
6.
7.
8.
77
S.No Compound Optically active Chiral Achiral Optically No. of
molecule molecule inactive Chiral Center
9.
Me
10.
Me
11.
12.
13.
14.
15. Hockey
78
CHEMISTRY
Q. If there is presence of given property then write () otherwise (×)

N
1. Et
Me
2.
3.
4.
5.
OH
H
6.
H
OH
7.
8.
79
9.
10.
11.
12.
13.
Me
H Cl
14. H Cl
Me
15.
80
CHEMISTRY
1. Find (m) meso compounds & optically active isomer (a) and total stereoisomer (a + m) of following compounds
S.N. Compound Meso(m) Active isomer(a) Total S.I.
Br
Cl
1.
Cl CH3
2.
Cl CH3
Cl CH3
3.
Br CH3
H3C
4.
H3C
CH3
5. H3C Cl
Br
CH3
6.
CH3
81
H3C CH3
7.
CH3 CH3
CH2
8.
CH2
9.
H3C CH3
CH3 H3C
H3C
10. CH3
CH3 H C
3
Br
11. H2C CH3
H3C CH3
12.
HO
13. Calculate DBE value of C5H10 & draw all possible structural isomer.
14. Calculate DBE value of C4H6 and draw all the possible structural isomers
82
CHEMISTRY
1.
CH3
2. Cl
Cl
CH3
3. Cl
CH3
Cl
Cl
CH3
4.
Br CH3
Br
Br Br
5.
Br
CH3 Cl SH
6. H3C CH3
Cl Br
7. H3C CH3
CH3
H3C
8.
Cl
83
Br
H3C
9. CH
Cl
CH
10. H3C
CH3
11.
Br Cl
12.
Cl Cl
Cl
CH3
13.
CH3
OH
CH3
14. H3C
OH
15. H3C
CH3
HO
84
CHEMISTRY
1. Find (m) meso compounds & optically active isomer (a) and total stereoisomer (a + m) of following compounds
S.N. Compound Meso(m) Active isomer(a) Total S. I.
Br
Cl
1.
Cl
2. NH
Cl Cl
Cl Br
3. H3C
CH3
Cl Br
4. Cl
H3C CH3
O Cl
5.
H3C
CH3
H3C O
O
|| NH
CH3 CH3
6.
NH ||
O
Br
7.
Br
Br
8.
Cl
H2C
9.
H3C CH3
Br
H3C
10. HN
CH3
85
CHEMISTRY
Std. 11th &12th CYCLOHEXANE CHAIR FORM DPP 22
1. Which of the following correctly lists the conformations of cyclohexane in order of increasing energy ?
(A) chair < boat < twist-boat < half-chair (B) half-chair < boat < twist-boat < chair
(C) chair < twist-boat < half-chair < boat (D) chair < twist-boat < boat < half-chair
(E) half-chair < twist-boat < boat < chair
2. Which of the following is the most stable conformation of bromocyclohexane ?
Br
H
(I) (II) (III) Br
Br H
H
H Br
(IV) (V)
H
Br
(A) I (B) II (C) III (D) IV (E) V
3. In the boat conformation of cyclohexane, the “flagpole” hydrogens are located :
(A) on the same carbon (B) on adjacent carbons
(C) on C-1 and C-3 (D) on C-1 and C-4 (E) none of the above
4. Which conformer is at a local energy minimum on the potential energy diagram in the chair-chair interconversion
of cyclohexane ?
(A) half-chair (B) planar (C) boat (D) twist-boat (E) fully eclipsed
5. The Keq for the interconversion for the two chair forms of methylcyclohexane at 25ºC is 18. What % of the
chair conformers feature an axial methyl group ?
(A) 95 (B) 75 (C) 50 (D) 25 (E) 5
6. Which of the following describes the most stable conformation of trans-1-tert-butyl-3-methylcyclohexane
(A) Both groups are equatorial (B) Both groups are axial
(C) The tert-butyl group is equatorial and the methyl group is axial
(D) The tert-butyl group is axial and the methyl group is equatorial (E) None of the above
7. Name the compound shown below.
Cl Cl
(A) trans-1, 2-dichlorocyclohexane (B) cis-1,2-dichlorocyclohexane

(C) trans-1, 3-dichlorocyclohexane (D) cis-1,3-dichlorocyclohexane
(E) trans-1,4-dichlorocyclohexane
8. What can be said about the magnitude of the equilibrium constant K for the following process?
(A) K = 1 (B) K > 1

(C) K < 1 (D) No estimate of K can be made
86
9. Column I Column II
(A) (P) cis-form
(B) (Q) trans-form
(C) (R) Keq is greater than one or equal to one when
compound undergo flip.
(D) (S) Keq is less than one when compound
undergo flip.
10. The equilibrium constant for the ring-flip of fluorocyclohexane is 1.5 at 25ºC. Calculate the percentage of the
axial conformer at the temperature.
11. Write correct order of stability of different form of following compound X with suitable reason.
(I) (II) (III) (IV)
12. Cyclohexane-1,4-dione is a polar compound, having dipole moment value of 1.2 D. If mol fraction of its chair
form is 0.80, what will be the dipole moment of twisted boat form?
13. Identify most stable form of given compound
(A) (B) (C) (D)
14. Dipole moment of a compound W– CH2– CH2–W is 1.5 D. If dipole moment of its gauche form is
6.0 D, what will be mol fraction of its anti form.
87
CHEMISTRY
Std. 11th &12th MIX QUESTIONS DPP 23
1. Which of following will not show geometrical isomerism ?
CH3 Cl Cl Br CH3 CH3 Br Cl

(A) C=C (B) C=C (C) C=C (D) C=C
H Br Br I H H Ph Cl
CH3
CH3
CH3 CH3
CH3
CH3
2. CH3
(I) CH3 (III) CH3
(II)
Which among these are isomers ?

(A) I and II (B) I and III (C) II and III (D) all of these
Paragraph for Question Nos. 3 to 5
Groups bonded by only a sigma () bond (i.e., by a single bond) can undergo rotation about that bond with
respect to each other. The temporary molecular shapes that result from rotation of groups about single
bonds are called conformations of a molecule. Each possible structure is called a conformer. An analysis
of the energy changes associated with a molecule undergoing rotation about single bonds is called
conformational analysis.
3. Most stable conformer of given compound is
HO—CH 2—CH2—F
F F OH H H H
H H H OH H H H
(A) (B) (C) (D)

H H H H H F OH
OH H H F
4. Most Stable conformer of
(A) (B) (C) (D)
5. Which of following equilibrum is not rapid at room temperature ?

CH3 CH3
H H H CH3
(A) (B)
H H H H
CH3 H
88
H
H H HH H
H
Br
(C) (D)
Cl Br H H
Cl H
H H
6. The lowest energy conformer of is

CH3 H
H
CH3 H H H
(A) (B) (C) (D)
H H CH3 H H H CH3 CH3
7. Match the column:

Column I Column II
OH
(A) (P) Conformation of maximum torsional strain

OH
(B) (Q) Conformation with strong intramolecular hydrogen bond
(C) (R) Highest boiling point
(D) (S) Conformation of minimum Vander Waal strain
89
Answer key
Answers of DPP No.-1
1. D 2. D 3. A 4. A 5. C 6. BC
7. CD 8. ABCD 9. BD 10. (a) 1°, (b) 2°, (c) 3°, (d) 3°, (e) 2°
11. (a) 2°, (b) 1°, (c) 3°, (d) 2°, (e) 2°, (f) 3°
Answers of DPP No.- 2
1.
(1) 0 (2) 1 (3) 2 (4) 0 (5) 1 (6) 2 (7) 1
(8) 0 (9 0 (10) 0 (11) 1 (12) 0 (13) 1 (14) 4
(15) 2 (16) 5 (17) 2 (18) 3 (19) 7 (20) 7 (21) 17
(22) 4 (23) 5 (24) 1 (25) 0 (26) 2
2. A  Q ; B  S ; C  P ; D R 3. A  R ; B  Q ; C  S ; D P

1. 4 2. 2.5 3. 7 4. 10 5. 10 6. 2 7. 7
8. 2 9. 10 10. 3 11. 3 12. 3 13. 4 14. 6
15. 0 16. 4 17. 3 18. 5 19. 4 20. 4 21. 2

1. C 2. A 3. C 4. B 5. B 6. B 7. C
8. D
1. Function group DBE
(i) ene, yne, ketone 5
(ii) aldehyde, 2° amine, 3° Amine, Amide, ene, ketone 6
(iii) ene, yne, anhydride, ketone and aldehyde 8
(iv) alcohol, naphthol, acid chloride, aldehyde 9
(v) ketone, alkene, anhydride 5
(vi) ketone, aldehyde, ene, yne, alcohol, amide, 1° amine, ester 11
2. C 3. (i) B, (ii) D, (iii) B, (iv) B, (v) A, (vi) B
4. (i) B, (ii) D, (iii) B, (iv) B, (v) B, (vi) B 5. (i) A, (ii) D, (iii) C, (iv) C, (v) B, (vi) B 6. (i) C
Answer of DPP No- 6

1. Position 2. Metamer & Position 3. Position 4. Chain
5. Identical 6. Functional 7. Functional 8. Functional
9. Different Compound 10. Different Compound
11. Ring Chain 12. Homologous
Answer of DPP No- 7
1. Position 2. Chain 3. Position 4. Metamer
5. Chain 6. Position 7. Position 8. Homomer (Identical)
9. Homomer (Identical) 10. Functional
Answers Key of DPP No.- 8

1. 1 2. 2 3. 3 4. 1 5. 4 6. 1 7. 2
8. 3 9. 0 10. 1 11. 3 12. 1 13. 1 14. 1
90
15. 1 16. 8 17. 4
Answer Key of DPP No. 9

If there is presence of given symmetry then write () otherwise (×)
P.O.S() C2 C3 Ci
(a)    ×
(b)    
(c)   × ×
(d)   × ×
(e)   × ×
(f)   × 
(g) ×  × ×
(h) ×  × ×
Answer Key of DPP No.-10

Compounds that will show Geometrical isomerism are :
2, 3, 6, 8, 9, 10, 11, 12, 13, 14, 15, 16, 19, 20,26, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43,
45, 46, 48, 49, 51, 53, 54, 55, 58,63, 65, 66, 67, 68, 70, 71, 72, 73, 76, 78, 80, 81, 82, 83, 84, 89, 90, 92, 93,
94, 95, 96, 97, 98, 99, 100, 103, 104, 105, 106, 107, 108, 109, 110
Answer of DPP No- 11
COOH
COOH OCH3
1.
Bongkrekic acid
COOH
2. A 3. C 4. D 5. B 6. (a) 4, (b) 2, (c) 2, (d) 8, (e) 2, (f) 2]

7. D 8. D 9. AB 10. (a) E; (b) Z; (c) E; (d) Z
91
1. E 2. Z 3. E 4. Z 5. Z 6. E 7. E
8. Z 9. Z 10. E 11. Z 12. Z 13. E 14. E

1. 2 2. 8 3. 8 4. 8 5. 8 6. 6 7. 6
8. 2 9. 2 10. 2 11. 2 12. 2 13. 4 14. 8
15. 2 16. 4 17. 2 18. 4 19. 2 20. 6 21. 4
22. 8

1. Diastereomer 2. Diastereomer (ac & bc) ; Identical (ab) 3. Diastereomer
4. Diastereomer 5. Identical 6. Identical 7. Identical
8. Constitutional isomer 9. Diastereomer 10. Enantiomer

1. Enantiomer 2. Identical 3. Identical 4. Diastereomer
5. Diastereomer 6. Constitutional isomer
7. Enantiomer (bc) ; Diastereomer (ab) & (ca)
8. Identical 9. Enantiomer 10. Identical 11. Identical
12. Identical 13. Diastereomer 14. Enantiomer

1. Constitutional isomer 2. Identical 3. Constitutional isomer
4. Diastereomer 5. Enantiomer 6. Enantiomer
7. Enantiomer 8. Enantiomer 9. Other 10. Other
92
S.No Optically Chiral Achiral Optically No. of
active molecule molecule inactive Chiral Center
1. × ×   4
2.   × × 2
3.   × × 2
4. × ×   2
5. × ×   2
6.   × × 2
7. × ×   2
8.   × × 1
9.   × × 2
10. × ×   0
11.   × × 2
12.   × × 0
13. × ×   0
14.   × × 2
15.   × × 0

S.No Optically Chiral Achiral Optically No. of
active molecule molecule inactive Chiral Center
1. × ×   0
2.   × × 0
3.   × × 1
4.   × × 1
93
5.   × × 0
6. × ×   2
7.   × × 5
8. × ×   2
9. × ×   4
10.   × × 2
11. × ×   2
12. × ×   2
13. × ×   2
14. × ×   2
15. × ×   0

1. 0, 2, 2 2. 1, 2, 3 3. 0, 4, 4 4. 0, 0, 2
5. 0, 16, 16 6. 1, 2, 3 7. 0, 8, 8 8. 1, 2, 3
9. 0, 4, 4 10. 1, 2, 3 11. 0, 2, 2 12. 0, 4, 4
13. DBE = 1, str. isomers = 10 14. DBE = 2, str. isomers = 9

1. 1, 2, 3 2. 0, 4, 4 3. 1, 2, 3 4. 0, 16, 16
5. 0, 0, 2 6. 0, 32, 32 7. 0, 0, 3 8. 0, 4, 4
9. 0, 8, 8 10. 0, 4, 4 11. 1, 2, 3 12. 0, 16, 16
13. 0, 16, 16 14. 0, 16, 16 15. 1, 2, 3

1. 0, 4, 4 2. 0, 8, 8 3. 0, 16, 16 4. 0, 8, 8 5. 0, 4, 4
6. 1, 2, 3 7. 1, 2, 3 8. 0, 4, 4 9. 1, 2, 3 10. 0, 8, 8

1. D 2. C 3. D 4. D
5. E 6. C 7. D 8. C
94
9. A  PR ; B  QS ; C  PR ; D QR 10. 40%
11. IV > III > I > II 12. 6D 13. B 14. 0.75
1. D 2. A 3. B 4. B 5. C 6. B
7. (A) - R, (B) - Q, (C) - P, (D) - S
95
CHEMISTRY
Std. 11th &12th GRAPHICAL ANALYSIS OF REACTION DPP 1
Energy profile Number of T.S. Number of R.D.S step Number of steps
intermediate
1. E
A
B
reaction-coordinate
B
2.
A
3. B
A
C
4.
A B
C D
5.
C D
A B
6. E B
A C D E
96
CHEMISTRY
Std. 11th &12th TYPES OF SOLVENT DPP 2
S.No. Solvent Polar Nonpolar Protic Aprotic

(1) HOH
(2) MeOH
(3) OH
O
(4)
OH
(5) NH3
(6) R – NH2
O
(7)
acetone
O
S
(8)
dimethylsulphoxide
(DMSO)
H N
(9) O
dimethylformamide
(DMF)
(10) O
dimethylacetamide
(DMA)
–N – P – N –
N
(11)
Hexamethylphosphoratriamide
(HMPT)
97
O
(12)
tetrahydrofuran
(THF)
O
(13) (DIOXANE)
O
(14) CCl4
carbontetrachloride
(15)
(16)
(17) CH3 – NH2
O
O O
(18)
[9]crown[3]ether
(19) Me2S
O
(20) C – OH
(21)
Benzene
(22) H–F
(23) Et – O – Et
O O
O O
(24)
[12]crown[4]ether
98
CHEMISTRY
Std. 11th &12th DEHYDRATION OF ALCOHOL & REARRAGNEMENT DPP 3
OF CARBOCATION
1. Compare rate of dehydration (acid-catalyzed)
OH
OH OH OH
OH OH
| |
(a) (b) (c)
OH
| OH
|
(d) | OH (e)
OH
2. Predict the major product of acid-catalyzed dehydration of alcohols

(A) 2-pentanol
(B) 1-methyl cyclopentanol
(C) 2-methyl cyclohexanol
(D) 2, 2-dimethyl-1-propanol
3. Identify-Product
CH3 CH3 CH3

| H2SO4 | | H2SO4
(a) CH3 – C – CH2 (b) CH3 – CH2 – C – CH – CH3
 | 
| |
OH OH OH
OH
|
—CH2 – OH H3PO4 —CH – CH2 – CH3 H3PO4
(c) (d)
 
OH
| CH3
+
| H+
H
(e) (f) CH3 – CH2 – CH – C – CH3 
 | |
OH CH3
99
OH
|
OH H+ H
+
(g) (h) A+ B
 
CH3
H+
| +
H H A+B
H
(i) CH OH  (j) 
A+ B
3
|
OH
OH OH
(k) KHSO4 (l) | H2SO4

170ºC
OH OH
H2SO4 |
(m) (n) H2SO4

| 
CH3
CD3
| OH
OH
|
+ +
H H
(o) (p)
 
OH
CH3
Cl
D D H
+
H3PO4
+
(q) D H (r) (s)
D  OH 

OH
4. Write-Mechanism
OH
OH
H
(a)
5°C
CH3
CH3
CH3 – CH2 – CH2 – CH2 – C – CH2 – OH H
(b)  C = CH – CH2 – CH2 – CH2 – CH3
CH3
CH3
100
CHEMISTRY
Std. 11th &12th DEHYDRATION OF ALCOHOL & REARRAGNEMENT DPP 4
OF CARBOCATION
1. Which of following carbocation will undergo rearrangement ?

+ + |
CH2 |
| CH2
|
(a) (b) (c) (d)
+
+
+
| |+ |
+ +
(e) (f) (g) (h)
O
Ph +
| +
(i) CH2 – O – CH2 – CH2 – CH2 (j)
Ph 
(k) (l) | + (m) CH3CH2CH2+ (n) (CH 3 ) 2 CH CHCH 3
CH2 – C = O

(o) (CH 3 )3 C CHCH 3 (p) (CH3CH2)3CCH2+
(q) (r)

(s) C H 2  CH 2  CH 2 (t)
|
CH 3  CH 2  O
(u) CH 3CH 2CHCH

+ 3
101
CH2–OH

2. H (A)

(A) an heating isomerizes to (B). What is the strucutre of (B).

CH3 OH
(A) (B) (C) (D)
Ph—CH—Ph
CH2–CH2–OH 
3. H (A) , Major product (A) is

( major )
Ph—C—Ph Ph—CH—Ph
CH2–CH3 CH–CH3
(A) (B)
Ph
Ph—CH—Ph Ph—C—OH
CH–CH2 CH2–CH3
(C) (D)
OH

4. Reaction-1 H (A)

( major )

Reaction-2 H ( B)

OH ( major )

Reaction-3 H (C)
OH 
( major )
Sum of -hydrogen is (A + B + C) is.
 
5. (A) H (x) (B) H (y)
OH  OH 
102
OH  
(C) H (z) (D) H (p)
 
OH
Total number of products obtained in above reactions including minor products is (include stereoisomer)
x y z p
6. In which of following reaction rearrangement take place with change is carbon skeleton.
CH3
|  
(A) CH3 — C — CH2 (B) CH3 – CH2 CH2 (C) CH3 – CH – CH2 – CH2 (D) CH3 – CH– CH3
| |
CH3 CH3
7. Sum of -hydrogen in major product of the reaction.

OH
H
Reaction-1  (A)

OH

Reaction-2 H (B)

OH

Reaction-3 H (C)

OH

Reaction-4 H (D)

Sum of -hydrogen is A + B + C + D =
CH3 CH3
| | 
8. Reaction-1 CH3 — C — CH — CH3 H (A)
| 
OH
CH3
| 
Reaction-2 CH3 – CH – CH2 – CH2 – OH H (B)

CH3
CH3 | 
Reaction-3 CH – CH – CH2 – OH H (C)

CH3
Sum of -hydrogen in (A + B + C = )
103
9. In which of following reaction resonance stabilized product will form.
CH2–OH OH
H 
(A)  (B) H
 
CH3

(C) OH H (D) All

104
CHEMISTRY
Std. 11th &12th PINACOLE-PINACOLONE REARRANGEMENT DPP 5
O
CH3—CH—CH—CH3 H
Q.1   CH3—CH2—C—CH3

OH OH
Mechanism:–
+ +
(1) CH3—CH—CH—CH 3 +H  H2 O + CH 3—CH—CH—CH 3
:
:O–H O–H O–H
+
s CH3 — CH 2—C—CH 3  CH3 — CH 2—C—CH 3
:
O—H O—H
+
CH3 CH3
Q.1 H 
Et — C — C —Et 

OH OH
Ph
Q.2 H 
Ph— C — CH 2 

OH OH
OH OH
H H
Q.3 H 


OH OH
CH3 CH3
Q.4 H 


OH OH
Q.5 H 

CHO
3 C—C— 
H H
OH OH
Q.6 H 


105
OH OH
Q.7 H 


Diazotization of primary amine:–

 NaNO2
R — NH2   R — N  N :  
 R  N2
HCl
Mechanism:–
(1) NaNO2 + HCl  H—O—N=O + NaCl
:
(2) H — O — N = O + H H2O + N=O
+
H H H
:
:
:
(3) R—N: + N = O  R—N — N = O  R—N—N = O—H
:
H H
H
: :
R—N= N—O—H
 H H
:
:
N2  R  R — N  N :  R—N

:
 R—N 
=N + O = N—O:
H H
Demjanov Reaction:–
OH NH2 O
2
NaNO
CH3 — CH—CH—CH3 
HCl CH3 — C—CH2—CH3
Mechanism:–
OH NH2 OH
2
NaNO
(1) CH3 — CH—CH—CH3  CH3 — CH—CH—CH3 + N2
HCl
O OH
H + CH3 — C—CH2—CH3  CH3 — C—CH2—CH3 
OH NH2
NaNO
2 _ _ _ _ _ _ _ _ _ _
Q.1 CH — CH — —OCH3 
HCl
NH2
NaNO2
Q.2   __________
HCl
OH
106
NH2 OH
NaNO2
Q.3   __________
HCl
OH NH2
NaNO2
Q.4 CH3 — CH —CH—   __________
HCl
SbCl5
Q.5   __________

Cl O—H
OH
Br
AlBr3
Q.6   __________

AgI
Q.7   __________

I O—H
OH
aq. AgNO3
Q.8   __________
I
107
CHEMISTRY
Std. 11th &12th ELECTROPHILIC ADDITION REACTION & MARKONIKOV'S RULE DPP 6
Q.1 Compare rate of electrophilic addition on alkenes:–
(a)
(i) (ii) (iii) (iv)
CH = CH2 CH = CH2 CH = CH2 CH = CH2 CH = CH2

(b)
NO2 CN O – Me NH2
(i) (ii) (iii) (iv) (v)
COOH
(c)
(i) (ii) (iii) (iv) (v)
(d) Ph — CH = CH2 PH — CH = CH — Ph
(i) (ii)
Q.1 HI  _ _ _ _ _ _ _ _ _ _
CH2 = CH2 
Q.2 HBr
CH2 = CH2  __________
Q.3 HI
 __________
Q.4 HI
C = CH2  _ _ _ _ _ _ _ _ _ _
Q.5 HI  _ _ _ _ _ _ _ _ _ _

Q.6 HI  _ _ _ _ _ _ _ _ _ _

Q.7 HCl  _ _ _ _ _ _ _ _ _ _

O
108
Q.8 HI  _ _ _ _ _ _ _ _ _ _

Q.9 HI  _ _ _ _ _ _ _ _ _ _
(Ph)2 CH—CH—CH=CH2 
Me
Q.10 HBr
C = CH—Ph  _ _ _ _ _ _ _ _ _ _
Q.11 HCl  _ _ _ _ _ _ _ _ _ _

Q.12 HBr
 __________
Q.13 HCl  _ _ _ _ _ _ _ _ _ _
CH2 = CH — Cl 
HCl(2eq.)
Q.14 CH  CH   __________
HCl(2eq.)
Q.15 CH3 — C  CH   __________
Q.16 HCl  _ _ _ _ _ _ _ _ _ _

dil.H2SO4
Q.17   __________
H /H2O
Q.18   __________
Q.19 H /R–OH  _ _ _ _ _ _ _ _ _ _

H /H2O
Q.20   __________
Me
HCl  _ _ _ _ _ _ _ _ _ _
Q.21 H D 
CH = CH2
D /D2O
Q.22   __________
O
H
+ H
Q.23 __________
109
Q.24 HBr
 __________
Q.25 HCl  _ _ _ _ _ _ _ _ _ _
CH  C — CH2 — CH = CH2 
Q.26 HCl  _ _ _ _ _ _ _ _ _ _
CH  C — CH = CH2 
Q.27 H
HO — CH2 — CH2 — CH2 — CH = CH2  __________
MeOH
OH
Q.28 H /MeOH  _ _ _ _ _ _ _ _ _ _

CH2= CH—CH—CH=CH2 
Q.29 H  _ _ _ _ _ _ _ _ _ _

O
H
110
CHEMISTRY
Std. 11th &12th OXYMERCURATION-DEMERCURATION DPP 7
OXYMERCURATION-DEMERCURATION (OMDM)
OMDM is a hydration process of alkene according to Markovnikoff’s rule with no rearrangement of cyclic
mercuinium ion. In oxymercuration, the alkene is treated with mercuric acetate in aqueous tetrahydrofuran
(THF). When reaction with that reagent is complete, sodium borohydride and hydroxide ion are added to the
reaction mixture.
( i ) Hg( OAc ) ,H O,THF
R–CH = CH2       
2 2
R  CH  CH 3
( ii ) NaBH 4 ,HO ¯
|
OH
AcO¯ = CH3COO¯
Mechanism for oxymercuration:

OAc
OAc +
Hg
H2O
CH3CH = CH2 + Hg — OAc CH3CH — CH2 CH3CHCH2—Hg—OAc
+
OH
+ AcO¯
H
¯OAc
CH3CHCH2—Hg—OAc
OH + AcOH
Sodium borohydride (NaBH4) converts the carbon-mercury bond into a carbon-hydrogen bond. Because the
reaction results in the loss of mercury, it is called demercuration.
NaBH
4 
CH3CHCH2 — Hg—OAc   CH3CHCH 3 + Hg + AcO¯
HO ¯
| |
OH OH
1. Identify the product of the following reaction.
CH3
( i) Hg( OCOCH )  CH OH
3 2
     3 

(i) (
i ) Hg ( CF3COO ) 2 ,CH 3OH
  (ii) ( ii) NaBH 4 ,OH
( ii ) NaBH 4 ,HO ¯
(i ) Hg( OAc ) ,H O
22 (i ) Hg( OAc ) ,H O
(iii)     (iv) 2
    2
( ii ) NaBH4 ,OH (ii) NaBH4 ,OH
CCH
OH 
(i ) Hg( OAc )2 ,H2O
    (i ) Hg( OAc )2 ,H2O
    
(v) (ii ) NaBH4 ,OH
(vi) (ii ) NaBH4 ,OH
2. How could each of the following compounds be synthesized from an alkene by OMDM?
OH OCH2CH3 CH 3 CH 3
| |
(i) (ii) (iii) CH 3CCH 2CH 3 (iv) CH 3CCH 2 CH 3
| |
OH OCH 3
111
CHEMISTRY
Std. 11th &12th HYDROBORATION - OXIDATION DPP 8
HYDROBORATION-OXIDATION :
Hydroboration has been developed by brown as a reaction of tremendous synthetic utility because alkyl
boranes are able to undergo a variety of transformation. Hydroboration is a one step, four centre, cis addition
process in accordance with M. rule but after oxidation it seems to be appear to violate M.rule.
OH¯ ,H2 O2 , H2 O
Hydroboration oxidation
CH3CH2CH2OH
(i ) BH THF CH3 COOH
CH3CH = CH2  3   (CH3CH2CH2)3 B Hydroboration reduction
CH 3CH 2CH 3
AgNO3
Dimerisation
CH 3CH 2CH 2
CH 3CH 2CH 2
Mechanism of Hydroboration:
H H
+ 2
CH3CH=CH2  CH3—C—C—H  CH 3CH 2 CH 2 (CH3CH2CH2)3 B
|
H—BH2 BH 2
H BH2
— an alkylborane
More stable
transition state
Mechanism of oxidation :
HOOH + HO¯  HOO¯ + H2O
112
1. Identify the product of the following reaction.
BH ,THF
( i ) BH ( i ) BH 3 

(i) CH2 = CH2  3  (ii)  3  (iii) H2O / OH
(ii ) HO ¯,H 2O 2 , H 2O (ii ) HO ¯,H 2O 2 , H 2O
BH ,THF BD3, THF

3 

(iv) H2O / OH
(v) CH3COOH
BH3, THF
CH3COOD
BT3, THF
CH3COOD
CCH
(i ) BH ,THF
 3 i  BH3 i  BH3
(vi) (vii)   (viii)  
(ii ) H2O2 / HO  ii H2O2 , HOO– ii H2O2 , HOO–
i  BH3
(ix)   (x)
ii H2O2 , HOO–
(i) BH (i) BH
   3    3
(xi) ii H2O2, HOO– (xii) R – CC–R ii H2O2, HOO–
(i) BH (i) BH
(xiii) CH3 – C  CH    3 (xiv)    3
ii H2O2, HOO– ii H2O2, HOO–
(i) BH
3
(xv)       
ii H2O2, HOO–
2. What alkyl borane is formed from hydroboration of each alkene ?
(A) (B) (C) (D)
3. Draw the products formed when each alkene is treated with BH3 followed by H2O2, HO O– include the
sterochemistry at all stereogenic centres.
(A) (B) (C) H3C (D)
4. What alkene can be used to prepare each alcohol as the exclusive product of a two step hydroboration–
oxidation sequence?
(A) (B) (C)
113
(i) Hg (OAc)2, H2O
(A)
(ii) NaBH4
5.
(i) BH3, THF
(B)
(ii) H2O2
(i) Hg (OAc)2, MeOH No. of products

(A) (Including stereo)
–
O
(ii) NaBH4,OH
6.
(i) BH3, THF No. of products
(B) (Including stereo)
(ii) H2O2
(i) BD3 . THF

(A)
(ii) H2O2
7.
(i) Hg (OAc)2 MeOH
–
(B)
O
(ii) NaBD4, OH
114
CHEMISTRY
Std. 11th &12th ELECTROPHILIC ADDITION REACTION & DPP 9
MARKONIKOV’S RULE
Q. Identify product including stereo chemistry
CH3 CH3 H O
1. 3 10. Ph – CH = CH – CH3 H O
3
CH3 11. H O
3
2. H O
3
CH3
H O
CH3 CH2CH3 12. 3
3. H O
3

13. H3O
  (x)
CH3 (major )
4. H O
3 Number of alcohol only.
CH2CH3
H3O 
14.  
5. H O
3
CH3
6. H O
3 CH2
CH3 H3O 
15.   A + B
7. CH3 – CH = CH2 H O
3
8. CH3 – C  C – CH3 H O OH
3 16.
H O
9. 3
115
CHEMISTRY
Std. 11th &12th ELECTROPHILIC ADDITION REACTION & DPP 10
MARRKONIKOV’S RULE
1. The alkene limonene has the following structure,
What product results from the reaction of limonene and chlorine water?
(A) (B) (C) (D)
2. Major product obtained in the following reaction r1, r2 and r3 in respectively is

HBr
CH3 r1
H2O
HBr
r2
CH3OH
HBr
r3
D2O
OH OD OCH3 OH OCH3 OD
CH3 CH3 CH3 CH3 CH3 CH3
(A) , , (B) , ,
Br OH
CH3 CH3
(C) in all reaction (D) in all reaction
Br
3. 2  W , W is
CH 2Cl2
(A) (B)
(C) (D)
4. Which of the following species is an intermediate in the reaction shown below :

Br
Br / H O
2
2
OH
116
(A) (B) (C) (D)
+O
Br+ O Br–
H
Br
2  Products obtained in this reaction are
5. 
CCl 4
Me
(A) Diastereoisomers (B) Enantiomers
(C) Positional isomers (D) Single meso compound
6. Which of following is most reactive toward Bromination
(A) (B) (C) (D)
7. Gases liberated at the surface of anode and cathode respectively in kolbe's electrolytic syntheis will be :
(A) H2, CO2 (B) CO2, H2 (C) NaOH, H2 (D) Only CO2\
(i) OSO 4
8.      (x)
(ii) NaHCO3 / H2O
Stereochemistry of product will be

(A) Optically active (B) Optically inactive (C) Racemic mixture (D) Meso
Br
CCl4
9. + Br2
Br
Correct statement regarding above reaction is
(A) Alkene will act as HOMO (Highest Occupied Molecular orbital).
(B) Br2 will act as LUMO (Lowest unoccupied molecular oribtal).
(C) Br2 will act as SOMO (Single occupied molecular orbital).
(D) Overall mechanism is anti addition.
Paragraph for question nos. 10 to 12 :
The halogens, Br2 and Cl2, add to alkanes. When the  electrons of the alkene approach a molecule of Br2
or Cl2, one of the halogen atoms accepts them and releases the shared electrons to the other halogen atom.
Therefore, in an electrophilic addtion reaction, Br2 behaves as if it were Br+ and Br¯, and Cl2 behaves as if it
were Cl+ and Cl¯.
+
:Br:
.. .. .. – .. ..
H2C = CH2 + :Br. . – Br
.. : H2C – CH2 + :Br .. : :BrCH
.. 2CH2Br
..:
1,2-dibromoethane
a bromonium ion a vicinal dibromide
Br2
10. cis-2-butene 
CCl4
How many products will obtained in this reaction

(A) 1 (B) 2 (C) 3 (D) 4
117
I
( X) ( Y) |
11. CH3 – CH = CH2 
 (A) 
 CH3 – CH – CH2
(intermediate) |
Br
Reagent (X) and (Y) in above reaction.
(A) X = I2 , Y = NaBr (B) X = Br2 , Y = NaI (C) X = NaBr, Y = I2 (D) X = I2, Y = Br2
12. Decreasing order of rate of reaction toward halogenation of alkene.
Me Me Me Me
(P) H2C = CH – CO2H (Q) Et – CH = CH2 (R) C=C (S) C=C
Et Me Me
H
(A) P > Q > R > S (B) S > R > Q > P (C) R > S > Q > P (D) P > R > S > Q
118
CHEMISTRY
Std. 11th &12th NON-CLASSICAL CARBOCATION DPP 11
CH3 CH3 Br2 , CCl4 CH3

1.   
Br2 , CCl4
13. H Br   
CH3
Br2 , CCl4
2.    CH
(cis)
CH3 CH
CH3 CH2CH3 CH3

Br2 , CCl4
3.   
CH3
CH3 14. Br2 , CCl4

H Br   
Br2 , CCl4
4.   
CH2CH3 CH
(trans)
CH
Br2 , CCl4
5.    CH3
CH3
Br2 , CCl4
6.    15. Br2 , CCl4
  
CH3
Br2 , CCl4
7. CH3 – CH = CH2   
Br2 , CCl4
16.   
COOH
Br2 , CCl4
8.   
COOH
Br2 , CCl4 Br2 , CCl4
9. CH3 – C  C – CH3    17.   
Br2 , CCl4
10.   
Br2 , CCl4
Br2 , CCl4 18.   
11. CH2 = CH – CH2 – C  CH   
H2O
12. + Br2 
Br2 , CCl4
19.   
119
CHEMISTRY
Std. 11th &12th NUCLEOPHILICITY & LEAVING GROUP ABILITY DPP 12
Identify nucleophilicity order in the following :
1. I– Br – Cl – F– in polar protic solvent
2. I– Br – Cl – F– in polar aprotic solvent
3. HO – H2O in protic solvent
..
4. NH 2– NH3 in protic solvent
–
5. HO – NH2 in protic solvent
6. H2O NH3 in protic solvent
7. CH3O, CN in protic solvent
8. HO – CH 3COO – in protic solvent
9. HO – SH – in protic solvent
10. (CH3)3N (CH3)3P in protic solvent
11. H2O H2S in protic solvent
12. CH 3COO – CH3O – in protic solvent
CH3
13. CH3OH CH3 – C – OH
CH3
–
14. O – in protic solvent
O
.. .. ..
N N N N
15. in protic solvent 16. in protic solvent
120
17. Leaving group order.
(a) I Br Cl F in polar protic solvent
(b) I Br Cl F in polar aprotic solvent
O O
|| ||
(c) CH3–S–O CH3 – C – O
||
O
O
||
(d) CH3 – C – O CH3 – O
O O
|| ||
(e) CH3 –S – O CF3 –S – O
|| ||
O O
O O
|| ||
(f) CH3 S–O NO 2 S–O
|| ||
O O
O O
|| ||
(g) CH3 S–O CF3 – S – O
|| ||
O O
(h) N2 HO
..
(i). HO H2O
..
(j) OH Cl
(k) –OTs –OBs
(l) HO CH3
121
18.
(i) Structure of E resemble with

(A) A (B) D (C) F (D) G
(ii) r.d.s step of reation ?

(A) A C (B) C  E (C) E  G (D) H  I
(iii) In above reaction.

(A) No. of T.S = No. of Intermediate – 1 (B) No. of T.S = No. of Intermediate.
(C) No. of T.S = No. of Intermediate + 1 (D) No. of T.S = No. of Intermediate + 2.
(iv) Structure of G resemblence with

(A) H (B) F (C) I (D) B
(v) Product of above reaction is
(A) G (B) I (C) F (D) C
19.
(i) How many Transition state is involved in above reaction

(A) 1 (B) 2 (C) 3 (D) 4
(ii) How many intermediate is involved in the reaction ?

(A) 1 (B) 2 (C) 3 (D) 4
(iii) Which step is r.d.s ?

(A) First step (B) Second step
(C) Third step (D) All step
122
CHEMISTRY
Std. 11th &12th SN1 REACTION DPP 13
Compound : (A) (B) More reactive towards SN1
I
1. I
Br
2. Br
Br CH2Br
3.
4. Ph CH2 Br Ph – CH – Br
CH3
CH3
CH3
H Br
5. H Br
Et
D
H Cl
Cl H
6.
H H
7. I I
Br
8.
Br
Br Br
9.
CH2Br Br
10.
Br
Br
11.
I Br
12.
13. [CH3 X] = 0.1 M [CH3–X] = 0.2 M

14. [Nu–] = 0.1 M [Nu–] = 0.2 M
123
CHEMISTRY
Std. 11th &12th SN2 REACTION DPP 14
Compound : (A) (B) More reactive towards SN2
I
1. I
Br
2. Br
Br CH2Br
3.
Ph – CH – Br
4. Ph CH2 Br
CH3
CH3 CH3
H Br H Br
5.
Et D
H Cl
Cl H
6.
H H
7. I I
Br
8.
Br
Br Br
9.
CH2Br Br
10.
Br
Br
11.
I Br
12.
13. [CH3 X] = 0.1 M [CH3–X] = 0.2 M

14. [Nu–] = 0.1 M [Nu–] = 0.2 M
124
CHEMISTRY
Std. 11th &12th SN1 & SN2 REACTION DPP 15
S.No. Compound Compare rate of SN2 Compare rate of SN1
1.
2.
3.
4.
5.
6.
7.
8.
9.
10. CH3 – O – CH2 – Br CH3 – CH2 – CH2 – Br
11.
12.
125
CHEMISTRY
Std. 11th &12th EXAMPLE OF SN1 & SN2 REACTION DPP 16
Q. Type of mechanism & more reactive reactant is
(1)
NaI
Br or Cl acetone
CH3
CH3 – CH2 – CH – CH2 or CH3 – CH2 – CH2 – CH2 – CH2 – Cl NaCN
(2) DMSO
Cl
Cl
(3) or CH3 – CH2 – CH2 – CH2 – CH2 – CH2 – Cl NaN3

ethanol
CH3 CH3
(4) CH3 – C – CH2 – Br or CH3 – C – Br EtOH
CH3 CH3
H2O
(5) Iso-butyl bromide or sec-butyl bromide
CH2–Cl Ph–SNa
(6) or
Cl
aq.KOH
(7) CH3 – I or CH3 – Br
EtOH
(8) or
Br Br
or KSH
(9) Br acetone
Br
Ph CH3
(10) Ph – C – Br or CH3 – C – Br EtOH
Ph CH3
126
CHEMISTRY
Std. 11th &12th EXAMPLE OF SN1 & SN2 REACTION DPP 17
Q. Identify the product(s) of the given reactions.

CH 3CH 2CH 2OH + HI
1. 1-propanol
a primary alcohol
OH
|

+ HBr
2.
cyclohexanol
a secondary alcohol
3. CH3CH2CH2CH2OH + PBr3  

pyridine
4.
5.
CH3
|
CH3CH2COH + HCl
|
6. CH3
2-methyl-2-butanol
a tertiary alcohol
CH3
|
7. CH3CCH2CH3 + HBr
|
OH

CH 3CHCH 2CH 3 + HBr
8. |
OH
9. xH

  
10. (i) ROH + HBr  (ii) ROH + HI  (iii) ROH + HCl 
(iv) ROH + PBr3  
pyridine
(v) ROH + PCl3  
pyridine
(vi) ROH + SOCl2  
pyridine

11. O H3O
 

12. H3O
 
127

13. H3O
 

14. H3O
 
H3O
15.  
O
H3O
16.  
O
1,4-dioxane
O 
H3O
17.  
O CH3
4-methyl-1,3-dioxane
H3O
18.  
19. CH3CH2 — O — CH3 excess HI A + B
20. HI/ HI/

CH3OCH2CH2CH3 A+ B C
21. CH3CHCH2OCH3 + HI  HI/

A+B C
CH3
CH 2OCH 2CH 2CH 3 HI HI

22.  A+B  C
NaOH conc .H

23. Ph – OH + Et – Br  ( A )  (B)  (C)
( excess )
O – CH3
24. xH
O – CH3 
O — CH2 — CH3 + H–Br

25.
CH3
26. CH3COCH2CH3 + HBr 
CH3
27. Give the major products that would be obtained from heating each of the following ethers with concentrated HI
128
:
CH3
|
(a) CH3CH = CHOCH2CH3 (b) —CH2O— (c) CH3CH2CH2OCCH2CH3
|
CH3
OCH3
(d) (e) (f) CH3
O O CH3
129
CHEMISTRY
Std. 11th &12th REACTION WITH PCl5,PCl3,SOCl2 DPP 18
Q. Write the product of the given reactions ?
PCl5 PCl5
(1) R – OH (2) Ph – CH2 – OH
O
PCl5
(3) CH3 – O – CH3 (4) PCl5
O
(5) PCl5
OH
O
(6) PCl5
OEt
O
(7) PCl5
O
(8) PCl5
Ph – C – CH3
O
PCl5
O
(9)
O
O
(10) PCl5
NH2
O PCl5
(11)
O–CH3 SOCl2
(12)
OH
PBr3
(13) OH
(14) Pent-1-yn-3-ol PBr3
130
CHEMISTRY
Std. 11th &12th WILLIAMSON ETHER SYNTHESIS DPP 19
WILLIAMSON ETHER SYNTHESIS

Passage : (1 to 11)
An important route to synthesize unsymmetrical ether is williamson ether synthesis. This reaction is an
example of Nucleophilic substitution reaction. (SN2 Reaction)
It involves the reaction generally between alkyl halide and alkoxide ion. 1° Alkyl halide and 1° Alkoxide ion
gives best yield of ether during this reaction.
1. Best method to prepare O – CH3 is
the combination of
KOH CH3I OH 
Na CH3I
(A) OH      (B)    
Na
Cl
(C) MeOH 
 (D) (A) & (B) both
2. NaH Me– I
H OH   (X)   (Y)

Identify (Y)
H OMe H OMe
(A) (B) MeO H (C) (D) None of these
3. Identify product EtO + Ph – CH2 – Cl 

O
(A) Ph (B) Ph (C) CH2 = CH2 (D)
O O Ph
4. Which of the following is an appropriate sets of reactant for the preparation of 1-methoxy-4-Nitrobenzene
Br ONa
(A) + CH3ONa (B) + CH3Br

NO2
131
ONa ONa
(C) + CH3Br (D) + EtONa

NO2 NO2
O
5. Suitable combination of reactant to prepare Ph
ONa
ONa + Br
(A) Ph (B) + Br
Ph
Br Br
(C) + KO (D) + NaO
Ph Ph
CH3
H OK EtBr
6.  Product
H CH3
Et
Correct stereochemical relationship between reactant and product will be
(A) Enantiomer (B) Diastereomer (C) Structural isomer (D) None of these
7. Which of the following can’t be prepared by willamson ether synthesis
(A) O (B) O
(C) O (D) O
8. Incorrect statement regarding williamson ether synthesis is

(A) Less hindered halide is used in this reaction
(B) Less hindered alkoxide ion is used in this reaction
(C) Mechanism of reaction will be SN2
(D) More hindered halide is used in this reation
9. Which of the following ether is not synthesied by willamson ether synthesis
(A) O–CH3 (B) O
(C) (D) O
O
132
10.  
RO Na + R – L ROR  + Na L
Rate of reaction will maximum when L is
(A) CF3SO3– (TRIFLATE ION) (B) CH 3 SO2 (p-Toluene sulphonate)
(C) Br– (D) I–
11. Identify the products
A KH TsCl C
OH
K
B
133
CHEMISTRY
Std. 11th &12th HYDROLYSIS OF ETHER (H3O+) DPP 20
S.No. Compound Structure of Product

(After reaction with dilute H3O+)
18
1. Ph – O – CH 3
2.
3.
OCH3
4. Ph – O
5. Ph – O – CH3
6.
O O
CH3
7.
O
8. Ph–O–CH2–CH2–CH–CH–O–CH2–CH3
CH3
9.
O
10.
O
11.
O
12. Ph – O – Et
13. O
14. O
15. Ph – O – CH = CH2
134
CHEMISTRY
Std. 11th &12th ETHER REACT WITH HI DPP 21
SNo. Compound Structure of Product Structure of Product

(When react with conc. HI) (When react with conc. HI excess)
1. O
2. O
O
3. Ph CH3
4. Ph O
O
5.
Ph Ph
6. PhOH
7. O
8. CH3 – CH2 – OH
9. O
O
10.
11. O
Ph
12.
Ph O
13. O – Et
14. Ph O
15. O
135
CHEMISTRY
Std. 11th &12th ETHER REACT WITH HI DPP 22
S.No. Compound Number of moles of HI consumed by the compound
1. Ph – OCH3
O
2.
Ph
O
3.
Ph
OCH3
4.
OCH3
5. O
O–CH3
O
6.
O
7. Et – O – Et
8. CH2O
9. CH3CH2CH2OCH2
10.
O
OCH 3
11.
CH3
12.
O CH3
136
CHEMISTRY
Std. 11th &12th ELIMINATION REACTION-E1 DPP 23
1. Sum of -hydrogen in products (P1 + P2 + P3 + P4 = ?).
CH3
+
(a) CH3 – CH2 – C – CH3 H P1

OH
CH3
+
(b) CH3 – CH2 – CH – CH3 – OH H P2

CH3
+
CH3 – C – CH – CH2 – OH H P3
(c) 
CH3 CH3
+
(d) CH3 – CH2 – CH2 – CH2 – OH H P4

2. Propose mechanisms for the following reactions.

OH H SO
2 4
(a) 
cyclopentanol cyclopentene
OH
H2SO4
(b) +

2-pentanol 1-pentene 2-pentene
OH
(c) H2SO4
+ +

CH3 CH3 CH3 CH2
2-methylcyclohexanol 1-methylcyclohexene 3-methylcyclohexene methylenecyclohexane
3. Sum of -hydrogen in products (P1 + P2 + P3 + P4 = ?).

CH2OH
OH
H3PO4
(a) P1 (b) H2SO4 P2


OH
OH
(c) H2SO4 P3 (d) H2SO4 P4
 
137
4. Dehydration of 2-methylcyclopentanol gives a mixutre of three alkenes. Propose mechanisms to account for
these three products.
CH3 CH3 CH3 CH2
H2SO4 + +
OH 
2-methylcyclopentanol major minor minor
5. Sum of -hydrogen in products (P1 + P2 + P3 = ?).
OH
OH
+ +
(a) H P1 (b) H P2
 
OH
+
H P3
(c) 

+ +
H P1 H P2
(a)  (b) 
OH OH
OH
+
(c) H P3

OH
OH
+ +
(a) H (b) H P2
P1 

+
(c) H P3

OH
138
CHEMISTRY
Std. 11th &12th E2 REACTION DPP 24
1. Compare the rate of elimination (E2) reaction of the following compounds.
(a)
Br
(b)
Br
Br Br
(c)
Br Br
D D
(d)
Br
Br
(e)
(f)
Br Br
(g) Br
Br
2. Predict the products of the following reactions. When more than one product is expected, predict which will
be the major product.
OH CH3
H2SO4 H3PO4 NaOCH3
(a) (b) (c) Br
 OH 
3. Predict the products of the following eliminations of vicinal dibromides with potassium iodide. Remember to
consider the geometric constraints of the E2 reaction.
Br Br Br
(a) CH3 – CH2 – CH – CH2 – Br (b) (c)
Br Br
H H
(d) (e) Br
H H
Br Br H
H Br
139
4. Predict the dehydrohalogenation product(s) that result when the following alkyl halides are heated in alco-
holic KOH. When more than one product is formed, predict the major and minor products.
(a) (CH3)2 CH – C(CH3)2 (b) (CH3)2CH – CH – CH3 (c) (CH3)2C–CH2–CH3
Br Br Br
CH3 CH3 (CH3)3C
(d) (e) (f)
Cl Cl
Cl
H D Cl
5. Explain why the following deuterated 1-bromo-2-methylcyclohexane undergoes dehydrohalogenation by the

E2 mechanism, to give only the indicated product. Two other alkenes are not observed.
6. Give the expected product(s) of E2 elimination for each reaction.

CH3 H
H
(a) NaOCH3 (b) NaOCH3
Br one product two products
H
H3C HH
H H D
Br
7. The following compounds show different rates of debromination. One reacts quite fast, and the other seems
not to react at all. Explain this surprising difference in rates.
Br
KI, acetone
(CH3)3C Br (CH3)3C
Br
KI, acetone
No reaction
(CH3)3C Br
8. Explain the reason for the difference in the major product for both given reaction.
Zaitsev product Hofmann product
H CH3 – H3C CH3 CH3–CH2 H
CH3 – C – C – CH2 OCH2CH3 C=C C=C
(a)
CH3CH2OH H CH3 H3C H
H Br H
71% 29%
H CH3 – H3C CH3 CH3–CH2 H

(b) CH3 – C – C – CH2 O(CH3)3 C=C C=C
(CH3)3COH H CH3 H
H Br H H3C
28% 72%
140
CHEMISTRY
Dear Students,
This DPP gives you an idea about products obtained in elimination reaction (including stereochemistry).
(A) Dehydrohalogenation
TOTAL PRODUCTS
Excluding Stereo isomer Including Stereo isomer
alc. KOH
1. Br
E2
alc. KOH
2. E2
Br
alc. KOH
3.
E2
Br
alc. KOH
4. E2
Br
Br
5. alc. KOH
E2
Br alc. KOH
6. E2
Cl
7. alc. KOH
E2
Cl
8. alc. KOH
E2
(B) Dehydration of alcohol
+
H
1. (E1)
OH
+
H
2. (E1)
OH
OH
+
3. H
(E1)
+
H
4. (E1)
OH
141
TOTAL PRODUCTS
Excluding Stereo isomer Including Stereo isomer
OH
+
5. Ph H
(E1)
OH
+
6. H
(E1)
142
CHEMISTRY
1. Treatment of a primary aliphatic amine with nitrous acid results in loss of nitrogen, N2 and formation of
substitution, elimination, and rearrangement products. Total 9 product(s) can formed by the treatment of
butylamine with nitrous acid.
CH3CH2CH2CH2–NH2 NaNO2,HCl
9 products
0-5ºC
Explain ?
2. As shown in the following equation, when (R)-1-deuterio-1-butanamine is diazotized with nitrous acid in
water, the alcohol product formed has the S configuration. (D = 2H)
D D
C C
H NH2 H
HO
CH3CH2CH2 CH2CH2CH3
(R)-1deuterio-1-butanamine
(a) Give the stereochemical configuration of the diazonium ion formed as an intermediate in this reaction.
Draw its structure.
(b) What mechanism for reaction of the diazonium ion with water is consistent with the stereochemical result
in the preceding equation ?
H
.. .. keto-enol .. .. ..
3. R – NH2 + HNO2 R–N–N=O:
.. R–N=N–OH..
tautomerism
A primary An N-nitrosamine (B)
aliphatic
amine
What is the name of the tautomer B ?

4. Draw the major product formed in each reaction
CH3 CH3
(1) CH3I(excess)
(1) ? (2) H C (2) Ag2O
3
NH2 (3) 
Br
(3) ? (4)
Cl NH2
143
CH3
CH3
– –
+ HO HO
(5) CH3 – CH – CH2 – N – CH2 – CH2 – CH3  ? (6) 
 + 
CH3 CH3 N
H3C CH3
H3C N(CH3)3
–
HO
(7) 

H3C
–
HO
(8) 
+ 
N
H3C CH3
(9) CH2 CH CH3

NH2
(10)
H2N
(11)
N
H
144
CHEMISTRY
Std. 11th &12th SUBSTITUATION VS ELIMINATION DPP 27
Identify Products :
 HI
H3 O
1. Ph – CH2 – O – Ph   (A) + (B)  (C)
H O
HI
2. CH3 – CH2 – O – CH2 – CH3 3  A+ B  (C)
OH
PBr3 alc . KOH
3.   (A)   (B)
Br
aq KOH SOCl 2 NaNH2
4.   (A)   (B)   (C)
Br
2Na NH 2
5.   (A)
Br
Br
2Na NH 2
6.   (A)
Br
OH
PCl 5 NaI
7.   (A) 
 (B)
acetone
Cl
aq. KOH H2SO 4
8.   (A)   (B)

Cl
Cl CH3 
3NaNH 2
9.  (A)
Cl
alc . KOH NaNH 2 Na NH2 CH3 I
10.   (A)   (B)   (C)   (D)
Cl
Cl Cl
H alc . KOH
H  NaNH2 2NaNH2 2EtI
11.  (A)    (B)   (C)  (D)
H H
145
Find value of (x) and (y)
Cl
( x ) NaNH2 ( y ) CH – I
1.    ( A )  3
 CH3 – C  C – CH3
Cl
Cl
( x ) NaNH ( y ) CH I
2. 2  ( A )   
   3  CH – C  C – CH
 3 3
Cl
Cl Cl
3. ( x ) NaNH2 ( y ) Ph – CH2 – I
       Ph – CH2 – C  C – C  C – CH – Ph
Cl Cl
146
CHEMISTRY
1. Tick mark the possible reaction shown by given compound ?
S. No. Compound SN1 SN2 E1 E2

(a)
Br
(b)
Br
(c) Cl
Cl
(d)
(e)
Br
Br
(f)
2. Calculate the total number of SN1 + E1 products including stereoisomers ?

S.No. Compound SN1 + E1 products
(a) Br
(b)
Cl
(c) Br
Br
(d)
Br
(e)
147
CHEMISTRY
1. Calculate the total number of SN1 + E1 products including stereoisomers ?

S.No. Compound SN1 + E1 products
Br
(a)
(b)
Br
Br
(c)
Match the column :

2. Column-I Column-II
Cl
(P) (1) SN1 reaction
Cl
(Q) (2) SN2 reaction
Cl
(R) (3) E1 reaction
(S) (4) E2 reaction

Cl
148
CHEMISTRY
Std. 11th &12th FREE RADICAL DPP 30
Q.1 Matrix
Reactions Number of dimerization product
(excluding stereoisomers)
(A) Na
CH3 — CH2 — Cl   (P) 1
Dry ether
Cl
(B) Na
  (Q) 3
Dry ether
14
(C) Na
H2C = CH — CH2 — Cl   (R) 6
Dry ether
14
(D) * Na
Cl  *  CH ) (S)
 + CH3 — Cl (H2C None
Dry ether 2
Q.2 Identify major products.

CH2Br
AlHg
(1) + 4 Na  (2)  
C2H5OH
Br
O
I Cl
I Cu Na
(3) I+  (4)  
120260C Dry ether
I
Cl
Br
Na  14 Na 
(5)  (6) 
DE D.E
Br
Na  Cl Na
(7)  (8)  
DE Dry ether
Br
(9) Na
 
Dry ether
Br
149
CHEMISTRY
Free Radicals:–
Wurtz Reaction:–
R — X  Na  R— R
ether
Mechanism:– (Free radical Mechanism)

(1) Na Na+ + e–

:
(2) R — X + e–  R + X
 
(3) R + R R — R
(Ionic Mechanism)
(1) Na Na+ + e–
:
(2) R — X + 2e–  R + X

 
:
(3) R + R — X R — R + X
Q.1 CH3 — Cl  Na  _ _ _ _ _ _ _

ether
Q.2 Na  _ _ _ _ _ _ _
Et — Cl 
ether
Q.3 Na  _ _ _ _ _ _ _
CH3 — Cl + Et — Cl 
ether
Q.4 Na  _ _ _ _ _ _ _
(Ph)3 CI 
ether
Q.5 Na  _ _ _ _ _ _ _
I 
ether
Na/ ether  _ _ _ _ _ _ _
Q.6 Cl Br 
Br
Q.7 Na/ ether  _ _ _ _ _ _ _
Br 
Q.8 Na/ ether  _ _ _ _ _ _ _ _ _


Cl Cl
Cl
Q.9 Na/ ether  _ _ _ _ _ _ _

Br
Q.10 Na/ ether  _ _ _ _ _ _ _
Cl Cl 
Cl Na/ ether  _ _ _ _ _ _ _
Q.11 Cl 
Q.12 Na  _ _ _ _ _ _ _ (fitting Reaction)
Ph — Cl 
THF
150
Q.13 Na  _ _ _ _ _ _ _ (Wurtz fitting)
Cl + Cl — CH3 
THF
Cl
Q.14 Na  _ _ _ _ _ _ _

ether
Cl
Zn  _ _ _ _ _ _ _
Q.15 CH2—CH2 
Br Br
Cl
Ag/Powder
Q.16 H—C—Cl   _______
Cl
Q.17 Na/ ether  _ _ _ _ _ _ _
CH2—CH=CH—CH2 
Br Br
I
Q.18 Na/ ether  _ _ _ _ _ _ _


Br
151
CHEMISTRY
Kolbe Electrolysis:–
O
NaOH R—R + CO2 + H 2
R — C —OH 
electrolysis
Anode Cathode
Mechanism:–
O O H
 —
(1) R — C —O—H + 

 R
OH  — C —O + O
H
Anode:–
O O
 –
(1) R — C —O—  R — C — O + e
O
 
(2) R — C — O  R + CO2 
 
(2) R + R R — R
Cathode:–
(1) 2H2O + 2e— 2O H + H2
electrolysis
Q.1 CH3 COOK  _ _ _ _ _ _ _
Q.2 NaOH
Et — COOH  _______
electrolysis
Q.3 NaOH
COOH  _______
electrolysis
HOOC
COOH
Q.4 NaOH
 _______
electrolysis
COOH
Q.5 KOH _______
COOH 
electrolysis
HOOC
electrolysis
Q.6 NaOOC COONa  _ _ _ _ _ _ _
electrolysis
Q.7 COONa  _ _ _ _ _ _ _
NaOOC
electrolysis
Q.8 KO3S SO3K  _ _ _ _ _ _ _ _ _
152
COOH NaOH
Q.9  _______
electrolysis
SO3H
COOH
Q.10 NaOH
 _______
electrolysis
COOH
SO3K
electrolysis
Q.11  _ _ _ _ _ _ _
SO3K
electrolysis
Q.12 KO3S  _ _ _ _ _ _ _
C C
SO3K
153
CHEMISTRY
Q.1 Identify the major product:-
CH2 — I
(1) Na
+  
Dry ether
Br Br
(2) + Na 

DE
Br Br
CH2 CH2
(3) Na
 
Dry ether
Br
(4) Na
 Se  (B)
 (A) 
Dry ether
Br
Br
(5) Na

D.E.
Br
Br
(6) Na
  Naphthacene
Dry ether
Br
CH2 — Br
(7) Na
  (A) + (B); (A) & (B) are isomer.
Dry ether
CH2 — Br
Br
* Na Na
(8) H2C = CH — CH2 — Cl  A + B + C (9)  
Dry ether Dry ether
Cl
154
Cl
Cl
(10) Na
  (11) Na
 
Dry ether Dry ether
Cl Br
Cl
(12) CH3 — CH2 — Cl + Na
  (13) Na
 
Dry ether Dry ether
2. Which of following is correct matching of energy profile diagram?
 
(1) CH3  Cl  CH3 — Cl E
rxn - coordinate
(2) hv  2Cl
Cl — Cl  E
rxn - coordinate
(3) CH3  + CH3   CH3 — CH3 E
rxn - coordinate
(4) Cl  + H — CH3  H — Cl +  CH3 E
rxn - coordinate
 KJ   KJ 
Bond energy  H  Cl  432   CH3  H  440 
 mole   mole 
3. When pentane is heated to a very high temperatue, radical reactions take palce that produce (among
other products) methane, ethane, propane, and butane. This type of change is called thermal cracking.
Among the reactions that take place are the following:-
(1) CH3CH2CH2CH2CH3  CH3  + CH3CH2CH2CH2 
(2) CH3CH2CH2CH2CH3  CH3CH2  + CH3CH2CH2 
(3) CH3  + CH3   CH3CH3
(4) CH3  + CH3CH2CH2CH2CH3  CH4 + CH3CH2CH2CH2CH2 
(5) CH3  + CH3CH2   CH3CH2CH3
(6) CH3CH2  + CH3CH2   CH3CH2CH2CH3
(a) For which of these reactions would you expect Eact to equal zero?
(b) To be greter than zero?
(c) To equal H°?
155
CHEMISTRY
1. Compound Number of monochloroproduct Number of monocloroproduct

(excluding stereoisomer)
1.
2.
3.
4.
5.
6.
7.
8.
9.
CH2
2.
1. Compound Number of Dichloroproduct Optically active product
(including stereoisomer)
1. 1-chlorobutane
2. R-2-chlorobutane
3. 3-chloropentane
4. R-2-chloropentane
5. S-2-chlorobutane
6. R & S-2-chloropentane
7. R & S-2-chloro butane
156
CHEMISTRY
Std. 11th &12th GRIGNARD REAGENT DPP 35
S.No. Reaction Product
1. PhMgBr + 2-propanol
2. PhMgBr + Ph – CH2 – OH
3. PhMgBr + CH3 – SH
4. PhMgBr + CH3 – C  CH 
5. PhMgBr + Acetic acid
6. PhMgBr +
O
7. PhMgBr + Ph – C – Ph
8. PhMgBr + CHO
9. PhMgBr +
CHO
10. PhMgBr +
11. CH3MgBr + Butanone 
12. CH3MgBr + 2-Pentanone 
13. CH3MgBr + 3-Pentanone

Q. Find the value of x in each reaction ?
OH OH
(a) x PhMgBr + (b) x PhMgBr + (c) x PhMgBr + CH=O
SH OH H OH
NH2 OH H OH
CH2–CCH OH HO H
CH2–O–CH3 CH2–OH
OH
157
CHEMISTRY
Identify product and compare rate of reaction ?
O
(a)
CH3MgBr + CH3 – C – H r1
O
CH3MgBr + Ph – C – H r2
CH 3MgBr + r3
O
O
(b) CH3MgBr + H – C – H r1
O
CH3MgBr + H r2
CH=O
(c) CH3MgBr + r1
CH=O
CH3MgBr + r2
CH3O
CH=O
CH3MgBr + r3
NO2
(d) O
PhMgMgBr + r1
O
PhMgMgBr + r2
PhMgMgBr + r3
O
(e) O
PhMgBr + r1
PhMgBr + Ph–CH=O r2
O
PhMgBr + r3
PhMgBr + r4
(f) PhMgBr + r1
O
PhMgBr + r2
O
PhMgBr + r3
O
158
CHEMISTRY
S.No. Reaction Product
O
1. PhMgBr + Ph – C – Cl
(excess)
O
2. PhMgBr + Ph – C – OEt
(excess)
O
3. PhMgBr + Ph – C – NH2
(excess)
O
4. PhMgBr + EtO – C – OEt
(excess)
O
5. PhMgBr + Et – S – C – Cl
(excess)
6. PhMgBr + Ph – C  N
(excess)
Cl
7. PhMgBr +
(excess)
OH
9. PhMgBr + CH3 – Cl 
10. PhMgBr + Br – Br 
159
CHEMISTRY
1. Propose the all suitable routes to prepare given alcohol by the help of grignard reagent ?
OH
(a) Et
(b)
OH
OH
CH3 CD3
(c)
CT3
2. Find the value of x ? (x = moleof RMgx consumed).
NH2
OCH3
OH
O O
OEt HS O
(a) (b)
Cl
Cl
O
O O–C–O–Ph
O O
160
CHEMISTRY
Q. X = Number of compound react with excess of RMgX to give 3º alcohol.
O O
(a) CH3 – C – O – Et (b) CH3 – C – Cl
O O
(c) Ph – C – O – Ph (d) Ph – C – O – CH3
O
O
O–C
O–C O
(e) O (f)
O
O
O–C
(g) O (h) Et – O – C – O – Et
CH3
NO2
O
(i) O=C=O (j) H – C – OPh
O
O
(k) H – C – Cl (l)
O Cl
(m) Ph – C – N O (n)
(o) (p)
O
(q) (r)
O O
161
(s) H – C  C – CH2 – CH2 – Cl
O
C
Et
(t) (u)
O NO2
O
O
(v) Ph – C – NH2 (w) S
O O
O–C O–C
S O
(x) (y)
H
(z)
CH3O
162
CHEMISTRY
O
||
1. PhMgBr + CH 3  C  Et    (P)
( ii ) H 
Major product (P).
OH Et OH
| | |
(A) Ph  C  Et (B) Ph  C  CH 3 (C) Ph  C  Ph (D) None
| | |
CH 3 CH 3 Ph
2. In which of the following reaction tertiary alcohol will be obtained as a product.
O
(A) C—CH3 + Et MgBr ( 
ii ) H 
O
||
(B) Ph  C  Cl + excess PhMgBr   
( ii ) H 
O
||
(C) Cl  C  O  Et + excess PhMgBr   
( ii ) H 
(D) All
3. Ph  CH  OEt CH
3MgBr
 (P) + PhMgBr (  (Q) End product (Q) is
ii ) H 
|
OH
O O
|| ||
(A) Ph  CH  CH 3 (B) Ph  C  Ph (C) Ph  C  H (D) Ph  CH  Ph
| |
OH OH
4. How many alkyl chlorides (without considering stereoisomers) would yield 2-methylbutane on conversion
into the Grignard reagent followed by treatment with absolute ethanol.
(A) 2 (B) 3 (C) 4 (D) 5
CH MgBr
5. CH 3CCH 2 CH 2 CH 2Cl 3 A, A is

||
O
CH 3
|
(A) CH 3CCH 2 CH 2 CH 2 Cl (B) CH 3CCH 2 CH 2CH 2CH 3
| ||
OH O
163
(C) (D)
CH MgBr (1 eq.)
6. 3   ?
The product is:
(A) (B)
(C) (D)
7. The number of moles of Grignard reagent consumed per mole of the compound
is:
(A) 4 (B) 2 (C) 3 (D) 1
8. CH2 = C = O (
i ) Br2
 C4H8O
( ii ) CH 3MgBr
( 2 equi )
(A) (B) (C) (D) All of these
Br
1. Mg / ether
9.         Product (s)
2. CH3CHCH2CH 3. H3O 
| ||
OH O
Select the product from the following
I: II : CH 3CHCH 2CH III :

| ||
OH O
(A) III (B) I, III (C) I, II (D) II, III
164
10. Nucleophilic addition of Grignard reagent cannot occur in
O O O O
|| | | || ||
(A) CH  C  C  CH (B) CH  C  CH  C  CH
3 3 3 2 3
O O O
|| || ||
(C) CH 3  C  CH 2  CH 2  C  CH 3 (D) CH
O
 Mg C–OMe
 HBr
11. OH  P1  P2  P3 P4 Mg
(Hg )
 P5
H Et 2O H 2O
 H 2SO4
( i ) C H MgBr
2 5
P7    P6
( ii ) NH 4 Cl
What is the total number of carbon atoms in P1 to P7 products.

(A) 91 (B) 92 (C) 93 (D) 94
12. Match the maximum number of CH3MgX consumed; given in Column 'II', when the substrates given in
Column 'I' reacts with it.
Column I Column II
(A) (P) 1
(B) (Q) 2
(C) (R) 3
Cl
(D) CH3 (S) 4
O O
165
13. Neither of these methods of making pentan-1,4 diol will work. Explain why not – what will happen instead?
(i) H – C – CH2–CH2–CH2–OH MeMgBr
  CH 3  CH  CH 2  CH 2  CH 2
|| followed by H  | |
O
OH OH
CH CHO
(ii) Br–CH2–CH2–CH2–OH Mg
 MgBr–CH2–CH2–CH2–OH 3

Et 2O followed by H
CH 3  CH  CH 2  CH 2  CH 2
| |
OH OH
14. What is the product in the following reactions.
(a) CH
3MgBr
 A

(b) PhMgBr + CH 2  C  CH 2   B
| |
Br Br
(c) CH 2  (CH 2 ) 3  CH 2  CHO (
i ) Mg / ether
  C
| ( ii ) NH 4Cl
Br
15. Identify unknown.
(a) HBr
 A
(b) COOEt (

i ) CH 3MgBr ( excess )
   B
| (ii ) H  
COOEt
(c) HNO
2  C

(d) H D

166
CHEMISTRY
Structure of compound Moles of RMgX consumed
O O
1.
Cl O
OEt
2. Cl
O
||
O – C – O – Ph
3.
HO CH2 – OH
O O
|| ||
4. HO – CH2 – C H2 – C – CH2 – C H2 – C – O – Et
CH2 – SH
5.
CH = O
O
6.
Cl O
O
||
O – C – CH3
7.
O–H
O
HO
CH3
8.
O O – Et
167
CHEMISTRY
O O Cl
Cl
H3C
O
O O
1. CH
N
O CH3
CH3
2.
O O
CH3
O H3C
OH H2N
H3C O
3. SH
O O
CH3
CH3
O
O
4.
HO
168
O
O
5.
Cl
6. O
H3C O
7. CH3
O O Cl
O
Br
H2N
CH
NH2
8.
O
O
CH3
9. O
H3C O
O OH
10.
169
CHEMISTRY
1. Identify products in given reaction.
O
(1) PhMgBr H  HBr
   
  (B)  (C)
(i) ( 2) H3O  (A)  CCl
 4
O
||
(i) CH MgBr H HBr
(ii) C  3   (B)  (C)
 (A) 
  CCl4
CH3CH2CH2 H (ii) H3O
(i) nbutylmagne sium bromide H  HBr

           (B)  (C)
(iii) Formaldehyde (ii) H3O  (A)  CCl
 4
(i) Ethyl magnesium bromide

        
(iv) 2-Pentanone (ii) H3O
A+ B
O
(i) CH MgBr 
 3 
 H
 (B) 
3 O
(v) (ii) H3O  (A)  (C)
 Zn
O
(i ) PhMgBr
(vi)    A + B
(ii) H3O
Br
O
||
Mg (i) Ph – C – H Cold. KMnO
4  (C)
(vii) (A) (B)  
(ii) H O3
O
||
H3O
(viii) C — H + PhMgBr   (A)
(excess)
O O
|| || PhMgBr
(ix) C – CH2 – C – H   (A)
O
||
(i)PhMgBr
(x)    (A)
(ii) H3O
170
O
HO
H (i) CH MgBr
3 
(xi)    (A)
(1mole)
(ii) H3O
2. Identify products :
O O
|| (i) 2EtMgBr ||
    (i) 2CH3MgBr
(i) CH3 – CH2 – CH2 – C – Cl (ii) H3O
(ii) CH3 – C – OEt    
(ii) H3O
O
O
|| (i) PhMgBr ( excess) (i) PhMgBr ( excess)
O 
        
(iii) Et – O – C – O – Et (ii)H3O
(iv) (ii) H3O
O O
(i) PhMgBr ( excess ) —N (i) PhMgBr ( excess )
O O       N —      
(v) (ii) H3O  (vi) (ii) H3O
O O O
|| (i) PhMgBr ( excess ) || ||
      (i) PhMgBr ( excess )
(vii) Et – O – C – Cl (ii) H O
(viii) Ph – C – O – C – Ph      

3 (ii) H3O
O O
|| (i) PhMgBr ( excess ) ||
CH3 – C – S – Et       (i) PhMgBr ( excess )
(ix) 
(ii) H3O
(x) Et – S – C – S – Et      

(ii) H3O
O
||
(i) PhMgBr ( excess )
(xi) Et – O – C – S – Et      
(ii) H3O
171
CHEMISTRY
Std. 11th &12th OZONOLYSIS DPP 44
OZONOLYSIS : The reaction of alkene or Alkyne with ozone (O3) followed by hydrolysis is known as ozonolysis.
It is of two types : (I) Reductive ozonolysis  In presence of reducing agent
(II) Oxidative ozonolysis  In presence of oxidising agent
Reducing agents : Zn, H2O or Zn, CH3COOH or (CH3)2S or (Ph)3P etc.
Oxidising agents : H2O2 or R  C  O  O  H or Ag2O etc.
||
O
R R’ R O R’ H  R
O3 3O/Zn
C=C C C Reductive C=O + R’–C–H
step I
R H –70°C R H ozonolysis R
O O O
Oxidative [SCT- Cut the double bond

Example 1 : ozonolysis H2O2 and paste two oxygen atoms
and vice versa]
R–C–R + R’–C–OH
O O
Mechanism :
R
– R
R R O R C O R’
O –
C 
O C O + C=O
+ O R 
C R’ C O H
R’ H O
H
R
R
O – R—C—O
C O
R  O
R’ R–C–R + R’–C–H
O
O=C C
H R’ O O
H
Note : In case of oxidative ozonolysis aldehyde (not ketone) further undergoes oxidation which gives
acid as product.
172
(i) O3
Example 2: R—CC—R’ R—C—C—R’ Product is vic
(ii) Zn, H 2O
dicarbonyl compound
Reductive O O
ozonolysis
(i) O3 (ii) CH3 C–O–O–H
O
Per acid
R—C—OH R’—C—OH (Products are carboxylic acid)
+
O O
1. Give the product of the following reaction.
(i) H2C = CH2 (

i ) O3
 (ii) CH3–CH = CH2 (
i ) O3

( ii ) Zn / H 2O ( ii ) Zn / H 2O
CH 3
|
(iii) (
i ) O3
 (iv) CH 3  C  CH 2 (
i ) O3

( ii ) Zn / H 2O ( ii ) Zn / H 2O
(v) (
i ) O3
 (vi) (
i ) O3

( ii ) Zn / H 2O ( ii ) Zn / H 2O
H
3 (i) O
(vii) H2C=CH–CH2–CH=CH–CH3  
( ii ) Zn / H 2O
2. Find out the structure of reactant.
O
(i) X ( i ) O3
 O + HCHO (ii) X (
i ) O3
 O
( ii ) Zn / H 2O ( ii ) Zn / H 2O
C10 H12
O
O
CH3 H
( i ) O3
(iii) X  + C=O + C=O
( ii ) Zn / H 2O
H3C H
O
O
(iv) X ( i ) O3
+ O (v) C6 H 4 ( i ) O3
 C3H2O3
( ii ) Zn / H 2O (X) (ii ) Zn / H 2O
H H
173
O O
(i) O
(vi) X 3  + HCHO
( ii ) Zn / H 2O
C12 H18
O
O
(i) O
O
(vii) X 3  + O=C=O + O + HCHO
( ii ) Zn / H 2O
C12 H18
H
O
(viii) X ( i ) O3
O+ (ix) X ( i ) O3
 CH 3  CH 2  C  H
( ii ) Zn / H 2O ( ii ) Zn / H 2O ||
O
O
H
(x) X (
i ) O3
 O + O (xi) X (
i ) O3

( ii ) Zn / H 2O H ( ii ) Zn / H 2O
O
3. Give the ozonolysis product of the following.
O3
(i)  ?
Zn / H 2O
How many species are found
(ii) O
3/

Zn / H 2O
How many species are found.
H
O3 (  )
(iii) X  3 O C H
Zn
4. How many ozonoid structures (including stereoisomers) are possible in given reaction.
3 O
(a) CH2 = CH2 Zn

/H O 2
3 O
(b) CH3 – CH = CH – CH3 Zn

/ H2O
3 O
(c) CH3 – CH = CH2 Zn

/ H2O
174
CHEMISTRY
Std. 11th &12th HYDROXYLATION DPP 45
11. Cold dil. KMnO 4

CH2 = CH – CH2 – C  CH 
CH3 CH3   
1. Cold dil. KMnO 4
   

   
CH3
2. Cold dil. KMnO 4
   
CH3
CH3
CH3 CH2CH3 Cold dil. KMnO 4
3. Cold dil. KMnO 4 13. H Br    
   
CH
CH3 (cis)
4. Cold dil. KMnO 4 CH
   
CH3
CH2CH3
CH3
5. Cold dil. KMnO 4 14. Cold dil. KMnO 4

    H Br    
CH
(trans)
CH3 CH
6. Cold dil. KMnO 4
    CH3
CH3
7. Cold dil. KMnO 4

CH3 – CH = CH2    
15. ( X)
products
COOH
8. Cold dil. KMnO 4
   
COOH
H CH2
9. CH3 – C  C – CH3 Cold dil. KMnO 4

   
16. ( Y)
products

   
17. (X) isomer of C4H8 (alkene only) ( Y)

products
175
CHEMISTRY
Std. 11th &12th HYDROXYLATION DPP 46
S.N. Reaction Number of stereo isomers of product Relationship between product
(During the reaction) (if meso is formed then write meso)
2 Br
1. cis-2-butene 
CCl4
cold KMnO4
2. cis-2-butene  
2 D
3. cis-2-butene 

Ni
2 Br
4. Trans-2-butene 
CCl4
Cold
5. Trans-2-butene 
KMnO 4
2 D
6. Trans-2-butene 

Ni
CH3
Br
Cl 
 
2
7. H
CCl4
CH
||
CH2
CH3
Cold
8. H Cl 
KMnO 4
CH
||
CH2
CH3
2 D
9. H Cl 

Ni
CH
||
CH2
O
||
H2
10. 

Ni
176
CHEMISTRY
Std. 11th &12th OXIDATION OF ORGANIC COMPOUND DPP 47
Q. What is the major product of the given reactions ?
1.
(A) (B) (C) FCH2(CH2)8CH3 (D) No reaction
2.
(A) (B)
(C) (D)
3.
177
(A) (B) (C) (D)
4.
(A) (B) (C) (D) No oxidation
5.
6.
178
7.
(A) (B)
(C) (D) No oxidation
8.
(A) (B)
9.
179
10.
(A) (B) (C) (D)
11.
(A) (B) (C) (D)
12.
180
(A) (B) (C) (D)
13.
(A) (B)
14.
181
(A) (B) (C) (D)
15.
(A) (B) (C) (D)
182
CHEMISTRY
Std. 11th &12th GLYCOLIC BOND CLEAVAGE DPP 48
–HlO3 –HIO3
1. R – CHOH – CH2OH + HIO4 2. R – CHOH – CHOH – R + H IO4
– HlO3 –2HlO 3
3. R2C(OH) – CHOH – R + HlO4    4. R – CHOH – CHOH – CHOH – R + 2HlO4   
– HlO3 – HlO3
5.   6. CH2OH – CO – CH2OH + 2HIO4  
– HlO3
7. 8. CH2OH– CO – CH2OH + 2HIO4
9. – HlO3 10. – HlO3

R – CO – CO – R+ HlO4 RCHNH2 – CHOH – R+ HlO4
HlO 4
11. R – CHOH – CH2 – CHOH – R  
CH2OH – CHOH – CHOH – CHOH – CHO + 4HlO4

12.
Aldopentose
13.
5HlO 4
14.  

5HlO4
CH2OH – CHOH – CHOH – CHOH – CO – CH2OH
15.
Ketohexose (fructose)
MeO – CH
16. 17.
CHOH
3HlO4
CHOH O
CHOH
HC
CHOH
CH2OH
Methyl glucoside (II)
18. Cold dil. KMnO4 NalO4

CH2 (A) (C)
KMnO 4
19. CH3 – (CH2 )7 – CH  CH – (CH2 )7 – COOH  
NalO 4
Oleic acid
Ni – H Ni – H
20. (i) CH2 = CH2   (ii) HC  CH  (iii) Ni
–H

Room temp. Room temp. 100C, Pr ess.
Ni– H
(iv)     (v)
120 –150C, Pr ess
183
CHEMISTRY
Std. 11th &12th LiAlH4 & NaBH4 DPP 49
1. What is the major product of the following reaction ?
O
O
(i) LiAlH
  
4 || (i) DIBAL H
   

(a) NH2 ? (b)
(ii) H3O  CH 3 – C – Cl (ii) H3O
O O
|| (i) LiAlH4 || (i) LiAlH4
  
(c) CH 3 – C – Cl (ii) H3O
(d) CH3 – C – OH   

(ii) H3O
O
O (i) NaBH4 ||
||     (i) LiAlH
4
(e) (f) CH 3 – C – NH 2  

CH 3 – C – OCH 3 (ii) H3O (ii) H3O
O O
H NaBH / D O
4 3 H LiAlH / H O
(g)     (h) 4 
3 
O
O
||
(i) H NaBD / H O
4 3

(j) DIBAL H
(CH3)2CHCH2CH2 C – Cl 
   
O O
CH2CH3 (i) LiAlH (i) NaBH
4
   4
  
(k) N (l)
(ii) H2O (ii). H2O
O
(i) LiAlH
4
(m) O   
 (n) O LiAlH
4
(ii)H2O  
N Lactone
|
CH3
O O
O
(i) NaBH4 (i) LiAlH
4
    
(o)  (p) (ii) H3O 
?
OH (ii) H3O
Pyruvic acid O
O O O
(i) NaBH
4 (i) LiAlH
4
    
(q) (ii) H3O  (r) O (ii) H3O 
184
O
O
OEt
(i) NaBH ( excess ) (i) NaBH
(s) OCH3   4   (t)
4
  
(ii) H2O (ii) CH3CH2OH
O O
O (i) LAH( excess )

    

(u)
CHO (ii) H3O 
O
S ||
(i) MeMgBr (i) LAH( excess )
   
     

(v) (ii) H3O  ? (w) H H (ii) H3O 
O
||
C (i) LAH( excess ) O (i) NaBD
4
    
   
(x) CH3 H (ii) H3O  (y) (ii) H3O 
185
CHEMISTRY
Std. 11th &12th LiAlH4 & NaBH4 DPP 50
1. 2.
3. 4.
1. LAH, ether 1. LAH, ether

5. (i) Acid chlorides CH3COCl     (ii) Acid anhydrides (CH3CO)2O    
2. H3O 2. H3O
1. LAH, ether
(iii) Esters CH3 – CH = CH – COOC2H5     
2. H3O
6. 7.
8. (i) (ii)
NaBH4 NaBH4
9. CH3COCH2COOC2H5   10. C6H5 .CO.CH2 .CH2 .COOH   C
Ethyl   ketopen tan oate  – Benzoyl propanoic acid
NaBH4 NaBH4
11. CH3 .CO.CH2 .CH2 .CO.CH3   CH 12. CH2OH.(CHOH)4 .CHO   CH
Hexan  2, 5  dione Glu cos e
NaBH4 NaBH4
13. C6H5 .CH  CH – CHO   C 14. NC.CH2 .CH2 .CHO   NC
Cinnamalde hyde 3 Cyanopropi onaldehyde
NaBH4
15. R.CO.Cl   R 16.
Acid chloride
186
CHEMISTRY
Std. 11th &12th CATALYTICAL HYDROGENATION DPP 51
CH3 CH3 Ni / D2
1.  
 Ni / D2
10.  

CH3
2. Ni / D2
 

C  C – CH3
CH3
11. ( X)
CH3 products
CH3 CH2CH3 C=C
3. Ni / D2
 
 H H
CH3 C  C – CH3
12. H ( Y)
4. Ni / D2 products
 

CH2CH3 C=C
H CH3
5. Ni / D2
 
 CH3
C
CH3
6. Ni / D2
 
 C
CH3
13. ( X)
products
7. CH3 – CH = CH2 Ni / D2
 

H
C
8. CH3 – C  C – CH3 Ni / D2
 
 C
H3C H
9. Ni / D2 Ph
 
 H3C
14. C
C
H3C Ph
Ph CH3
15.
H3C Ph
187
CHEMISTRY
Std. 11th &12th CLEMMENSON REACTION DPP 52
CLEMMENSEN REDUCTION :
The reduction of carbonyl groups of aldehydes and ketones to methylene groups with amalgamated zinc and
concentrated hydrochloric acid is known as Clemmensen reduction.The mechanism summarized below
showing that reduction under acidic conditions often involves protonated species to which the metal offers.
O
||
Zn(Hg ) or Na(Hg )
C2 H 5  C  CH 3    C2H5 – CH2 – CH3
HCl
Mechanism of Clemmensen Reduction:
 OH
O  OH 2+
H Zn  Zn
C2 H5 — C — CH3 C2 H5 — C —CH3 + 2e C2H 5 — C —CH3

H–Cl
H  H
O
OH

H
C2 H5— CH —CH3 –H2O
C2 H5— CH —CH 3 C2 H5— CH —CH 3

Zn  Zn + 2e
2+
C2 H5— CH —CH 3 C2 H5— CH 2 — CH3 + ZnCl2

 H–Cl
OH
CHO
1. PhCOCH2 – CH2COOH  
Zn / Hg
2. Zn
Hg

HCl HCl
O
|| Zn ( Hg )
3. O Zn
/ 
Hg
 4. Ph  C  CH 3   
HCl HCl
188
O = C – CH3
5. Zn
( Hg
) 
 6.
Zn ( Hg )
O=C—CH3    (A)
HCl HCl
NO2
O O
Zn ( Hg )
7. Zn
( Hg
) 
 8.
C—CH = CH—C—OH HCl


HCl, H 2O
O
O
C2H5
Zn / Hg, C H OH
9. Zn
( Hg
)  ?
 10.
2 
    5 
HCl HCl, 24 h
O CH3
Zn, Hg
11. Me(CH2)5 CH = O 25
 
% HCl
12. Exception of clemmenson

(i) Diketo containing active methylene group when undergoes clemmenson reduction, unexpected product are
formed.
O O O
|| || ||
Zn ( Hg )
CH 3  C  CH 2  C  CH 3    CH 3  C  CH  CH 3
HCl |
CH 3
Mechanism:
 
O O O O
CH3—C— CH2— C— CH3  CH3—C—CH2— C—CH3 

 
O O
2e
H–Cl
189
O O
2e HCl


HCl
OH OH
Example Zn
( Hg
) 

HCl
O O
190
CHEMISTRY
Std. 11th &12th WOLF KISHNER REDUCTION DPP 53
WOLF-KISHNER REDUCTION
Wolf-Kishner reduction involves the conversion of carbonyl groups of aldehydes and ketones to methylene
groups by heating their hydrazones, semicarbazones or azines in the presence of strong base such as
C2H5ONa or NaOH.
O
NNH2
KOH , heat
N2H4       + N2
 H 2O HOCH 2CH 2OCH 2CH 2OH
( diethylene glycol)
propiophenone
hydrazone n-propylbenzene (82%)
O N–NH2 +
t-BuO¯ K
N 2H 4
 + N2
O
cyclohexanone CH3—S—CH3
cyclohexane (80%)
hydrazone
(DMSO, a solvent)
NH NH
 2 
2
 Ph–CH –CH

HO , or t BuOK 2 3
(Aldehyde + Ketone) (basic medium)

Mechanism of wolf-kishner
 
H
OH
  .. .. –OH 
R2C = N—NH 2 R2C = N—NH R2C — N = NH + H2O R2C — N=NH + OH
(I) (II)
H 
–H2O –N2  HOH 
R2 — C– N=N R2CH R2CH 2 + OH
1. To reduce ketone to CH2 best method is:
(i) Wolf-kishner (ii) Clemmenson (iii) LiAlH4 (iv) None

(i) N H
2 
4

(ii) KOH,heat
O O O
2. (
i ) H 2 NNH 2
  3. Zn(Hg)
(ii ) KOH , heat O 
HCl,H2O
191
O
C—CH3 Zn(Hg)
A
HCl,
OH
 
H2 N–NH2, OH,  H N NH , OH
4. B 5. 2   
2 


CHO
OH
O

H N NH , OH
6. 2   
2 


192
CHEMISTRY
Std. 11th &12th MOZINGO REACTION DPP 54
MOZINGO METHOD :
O CH 2 SH
R S R H
|| |
CH 2 SH Raney Ni C
R  C   C  
| H H 2 / Ni H H
H S de  sulfurisation
H
Cyclic thioacetal
Mechanism of Mozingo method
Protonation in acidic medium increases electrophilicity.

O O–H
+ +
H H
R—C—H R—C H—S—CH2—CH2 —S—H
H

H
OH OH

R—CH—S—CH2—CH2—SH R—CH—S—CH2—CH2—SH
H
H
S CH2
H H
O H  CH2 S CH2 

R—CH=S—CH2 H

R—CH—S—CH2—CH2—SH R—CH S
S S  H2 / Ni
  R–CH3
R—CH
Imp. Raney Nickel  H2 molecule is adsorbed on Ni.
O O
+ H + H
SH SH SH SH
(i) (ii)
Raney—Ni Raney—Ni
O
MeO H NNH , 
(i) HS SH, BF3 H 2  2
(iii) (ii) Raney-Ni (iv) triethylen e
glycol,KOH
O MeO
Conversion :
O O O O
(i) (ii)
H H D H H H CH3 H
193
CHEMISTRY
Std. 11th &12th HEATING EFFECT DPP 55
Reaction Product
O O
|| ||
(a) Ph–C–CH2–C–OH

O O
|| ||
(b) 
OH 
CH2—CO2H
|
(c) C=O 
|
CH2—CO2H
O
|| CO2H
(d) CO2H 
O
HO2C || CO2H
(e)

O
|| CO2H
(f) Ph–C–CH 
CO2H
O
|| CO2H
(g) 
|| CO2H
O
O
||

(h)
CO2H CO2H
194
Reaction Product
O
||
CO2H
(i)

O
|| +
(j) CH –C–CH –CN H3O
3 2 
O
||
CN
(k) H3O +

CN H O +
3
(l) CH 2 
CN
O
||
(m) H 2C = CH – CH 2 – CH 2 – C – OH 
O
||
(n) CH 3 – CH = CH – CH 2 – C – OH 
H C CO2H
|| 
(o) H C CO2H
(Maleic acid)
(p) H C CO2H
|| 
CO2H C
H
(Fumaric-acid)
195
CHEMISTRY
Std. 11th &12th HEATING EFFECT DPP 56
Compound Moles of CO2 evolve when
given compound undergo heating
OH
CO2H
(a)
CO2H

O
||
(b) HO2C CO2H
HO2C CO2H 
O
|| CO2H
(c) —C–CH
CO2H 
CN
CN H3O +
(d) CN 
CN
O O O
(e) || || ||
C–OH 
(f) 
N CO2H
CO2H
(g) 
N

(h)
CO2H
O
O
||
(i) CH –C–CH H3O +
3 2–CN 
196
CHEMISTRY
Std. 11th &12th SNAE REACTION & ESTERIFICATION DPP 57
ESTERIFICATION
Alcohols will react with carboxylic acids under acid catalysis. The acid (usually HCl, or H2SO4) reversibly
protonates a small percentage of the carboxylic acid molecules, and the protonated carboxylic acids are
extremely susceptible to attack by even a weak nucleophile such as an alcohol.
This tetrahedral intermediate is unstable because the energy to be gained by re-forming a C=O bond is
greater than that used in breaking two C–O bonds. As it stands, one of the leaving groups (R–,HO–, or RO–) is
very good. Once the oxygen atom of, say one of the OH groups is protonated, it becomes a much better
leaving group (H2O, pKaH – 2, instead of HO– , pKaH15). Loss of ROH. Loss of ROH from the tetrahedral
intermediate is also possible: this leads back to starting materials––hence the equilibrium arrow in the
scheme above. Loss of H2O is more fruitful, and takes the reaction forwards to the ester product.
Esters not only undergo acid hydrolysis, they also undergo base-promoted hydrolysis. Base-Promoted hy-
drolysis is called saponification.
H2O
 
Matrix -Match Type

1. Column I Column - II
(A) Saponification (P) H

+ CH3–OH 
H2SO
  4

(B) Trans-esterification (Q)
H2O
NaOH
 
(C) Esterification (R) H2O
(D) Acid Hydrolysis (S) 

H
 
(T) H

197
2. Most reactive alcohol towards esterification
(A) primary alcohol (B) sec. alcohol (C) ter. alcohol (D) all have same reactive
3. Most reactive acid towards esterification
(A) formic acid (B) methanoic acid (C) ethanoic acid (D) propanoic acid
4. 5.
6. + MeOH 7.
H SO
8. 9. 2 
4
10.
11. 12.
13.
Br
 2
 (A)
 i  KCN
   (B)
14. (C)
h iiH3O 
15. +
16. + (C)
198
CHEMISTRY
Std. 11th &12th SNAE REACTION & ESTERIFICATION DPP 58
Esterification DPP
1. Complete and balance equations for hydrolysis of each ester in aqueous solution. Show each product as it is
ionized under the indicated experimental conditions.
(a)
(b)
(c)
(d)
(e)
2. Complete equations for hydrolysis of these amides in concentrated aqueous HCl. Show all products as they
exist in aqueous HCl, and show the number of moles of HCl required for hydrolysis of each amide.
(a) (b)
3. Complete the following transesterification reactions. The stoichiometry of each is given in the problem.
(a)
(b)
199
4. Complete the following reactions. The stoichiometry of each reaction is given in the equation.
(a) (b)
5. Complete the following equations :
(a)
(b)
(c)
(d)
(e)
(f)
(g)
(h)
200
CHEMISTRY
Std. 11th &12th ALDOL REACTION DPP 59
Aldol Condensation
The -hydrogen of carbonyl compound is acidic due to the fact that the anion (also known as the enolate
anion) is stabilized by resonance.
In aqueous base, two acetaldehyde molecules react to form a -hydroxy aldehyde (aldol) as well as water.
The reaction is called Aldol condensation. The enolate ion is the intermediate in the aldol condensation of
aldehyde and ketone. Acetaldehyde for instance, forms a dimeric product aldol in presence of a dilute base
10% NaOH, KOH, Baryta, lime water.
–
O
OH / HOH 
2CH3CHO     CH 3  CH  CH 2  CHO   CH3 – CH = CH – CHO + H2O
5C
|
OH
-hydroxy butyraldehyde (Aldol) (Aldol condensation)
Mechanism :
H –
O
OH –
O
CH2— C—H CH2— C—H + H2O
O O (enolate ion) –
O
O O
–
O Slow
CH3— C—H + CH2— C—H CH3—C—CH2—C—H
O H O
H2O
–
O OH OH
–OH | –
O
CH3–CH=CH–CHO CH3–CH–CH–CHO –
CH3—CH—CH2—C—H + OH
(Aldol condensation)
–
O OHO
(aldol) O
Aldols are stable and may be isolated. They, however can be dehydrated easily by heating the basic reaction
mixture. Thus if the above reaction is heated the product is dehydrated to crotonaldehyde (2-butenal). Aldol
condensation take place in basic as well as acidic medium. In acid catalysed aldol condensation enol form
of carbonyl is the nucelophile in place of enolate.
1. Write the product and mechanism for given reactions.

(1) CH 3  CH 2  C  H Dil
NaOH
 (A) 
 (B)
||
O
201
O
(2) Dil
 NaOH
 (C)
(3) C6H5 – CH2– CHO Dil

 NaOH
 (D)
O

(4) Dil
 NaOH
 (E) 
 (F)

(5) C6 H 5  C  CH 3 Dil
 NaOH
 (G) 
 (H)
||
O
2. Identify the intramolecular aldol product?
O O
|| || 
(1) CH 3  C  CH 2  CH 2  C  CH 3 Dil
 NaOH
 (A) 
 (B)
O O
|| ||
(2) CH 3  C  CH 2  CH 2  CH 2  CH 2  C  CH 3 Dil
 NaOH
 (C)
O O
|| ||
(3) CH 3  C  CH 2  CH 2  CH 2  C  CH 3 Dil
 NaOH
 (D)
(4) Dil
 NaOH
 (E) 

(F)
O O
|| ||
(5) CH 3  C  CH 2  CH 2  CH 2  CH 2  CH 2  C  CH 3 Dil
 NaOH
 (G)

3. Find out the total number of aldol products (including and excluding stereo products) and write the IUPAC
name of products.
NaOH / HOH
(1) CH3–CHO + CH3–CH2–CHO   
5 C
NaOH / HOH
(2) C6H5 –CHO + CH3–CHO   
5 C
202
NaOH / HOH
(3) CH3–CHO + CH 3  C  CH 3  5 C

||
O
NaOH / HOH
(4) CH3–CH = O + CH 3  CH 2  C  CH 3   
|| 5 C
O
NaOH / HOH
(5) C6H5 – CHO + CH 3  CH 2  C  CH 3   
|| 5 C
O
4. Identify the structure of substrate?
O
Dil NaOH
(1) A   A=?
5 C
OH
OH
|
(2) A Dil
NaOH
 CH 3  C  CH 2 — C — CH 3 A=?
( 2 mole) 5 C
|| |
O CH 3
5. Complete reaction sequence :
–
O
(i) OH
(1) (
i ) O3
 (A)   (B)
( ii ) Zn / H 2O (ii) 
–
O
(i) OH
 
(ii) C H5CHO
(2) 6 (A)
(iii) 
O
O OH
–
O
(i) OH CH3 CH–CH3
(3) (A) + (B)  
(ii) 
OHO–
(4) (A)   
CH3
OH
203
O
–
O
(i) OH
(5) [X]  
(ii) 
O3 Ag
6. (A)  Ph – CHO + 2B  2 Oxalic acid.
(will not undergo
self aldol)
Structure of (A) is.

(A) Ph – CH = CH – CH = CH – CH3 (B) Ph – C  C – CH = CH – CHO
(C) Ph – CH = CH – C  C – CHO (D) Ph – C = CH – C  CH
|
CHO
204
CHEMISTRY
Std. 11th &12th CANNIZZARO REACTION DPP 60
CANNIZARO REACTION :
This reaction is given by aldehyde having no -hydrogens in the presence of conc. NaOH/ or KOH/ (50–60%)
O O
|| KOH ||
H  C  H  H  C  O O– + CH3OH

Mechanism 3rd order, rate  [HCHO]2 [OH ]
O O
–
|| ||
CH3 – OO +H –C –O – H CH 3OH + H – C – O O–
In the presence of a very strong concentration of alkali. 4th order reaction rate [HCHO]2 [OH–]2
– –
O
O O
– OO –
O O
OH OH
H–C H–C–H H–C–H
(I)
H OH O
–
O
–
O –O
O
O H H
–
H–C–H +C=O H–C + H–C–OO
(I)
O H O H
–
O
– H2 O –
O
O
HCH2 O From solvent HCH2 OH + OH
1. Which of following will not undergo Cannizaro reaction
(A) (B) (C) (D) Cl3C–CHO
CHO H
2. | conc
 . NaOH
 (A)  (B)

CHO
Product (B) is
O
||
CH 2  O  C
(A) H2C=CH–CO2H (B) (C) | | (D) H2C=C=O
CH 2  O  C
||
O
3. Cannizzaro reaction does not take place with
(A) (CH3)3CCHO. (B) (C) (D) CH3CHO.
205
NaOH
4. In the reaction (CH3)3CCHO + HCHO  
 A + B.
heat
the products (A) and (B) are respectively.

(A) (CH3)3CCH2OH and HCOO– Na+. (B) (CH3)3CCOONa and CH3OH.
(C) (CH3)3CCH2OH and CH3OH. (D) (CH3)3CCOONa and HCOO– Na+.
5. KOH
+ HCHO   (A) + (B)
(A) (B) + CH3OH (C) (D) (A) and (B) both

6. In the given Cannizzaro reaction - 2Ph – CHO OH
 Ph – CH2OH + PhCO2– the slowest step is :
(A) The attack of  OH at the carbonyl group (B) The transfer of hydride to the carbonyl group
(C) The abstraction of proton from the carboxylic acid (D) The disproportionation of Ph – CH2OH
7. In the cannizzaro’s reaction the intermediate that will be the best hydride donor ?
(A) (B) (C) (D)
8. Identify the products in the following disproportionation reaction :
2 ; 2
P Q R S
(A) D–CH2–OH
(B) CH3OH D–CH2–OH
(C) D–CH2–OH D–CH2–OH
(D) D–CH2–OH CD3–OH
206
Complete the reaction and Explain mechanism.
NaOD NaOD
(9) HCHO  (10) DCHO 
 
KOH KOH
(11) Ph–CHO + HCHO  (12) Ph  C  C  H 
 || | | 
O O
(13) Me–NO2 + HCHO KOH

(excess)
Write Mechanism :
CH2–OH
|  
(14) Me–CHO + HCHO KOH
 HO–CH2–C–CH2–OH + HCO2K
(excess) |
CH2–OH
207
CHEMISTRY
Std. 11th &12th HALOFORM TEST DPP 61
Q. Which of following give positive iodoform test.
O
O O Cl O
CH3
(1) H3C (2) H3C (3) (4)
CH3 NH2 H3C O Cl
CH3
O
O H3C
CH3 CH3
(5) H3C (6) (7)
O HO O
O CH3 O
O
NH CH3
OH
(8) (9) (10)
O
O
O
HO H CH3
O H OH
(11) (12) (13)
OH
O O CH3
CH3
(14) (15) CH3 (16) OH

H3C
O O
O
OH
(17) (18) (19)
O
208
O CH3
N
O
(20) (21) H3C (22)
CH3
O
OH
OH
H3C
(23) (24) H3C (25) CH3
CH3
O O HO
OH
CH3
CH3 H3C
H3C
OH
(26) H3C (27) (28)
O O CH3
H3C CH3 H3C CH3 H3C

CH3
(29) (30) (31)
O O O O O
OH O
CH3
O H3C H3C
H3C
(32) (33) CH3 (34)
OH OH
O O
OH
OH
OH CH3
(35) (36) CH3 (37)
H3C CH3
OH
209
H3C O CH3
CH3
CH3
(38) (39) (40)
O O
OH
O O
(41) (42) (43)
O O OH
OH
CH3
(44) (45) (46)
O
OH
O CH3 CH3
OH O
(47) (48) (49)
O
O CH2 HO CH2
OH
(50) (51) (52)
HO CH3
(53)
210
CHEMISTRY
Std. 11th &12th PERKIN CONDENSATION DPP 62
PERKIN CONDENSATION:
In Perkin reaction, condensation has been effected between aromatic aldehydes and aliphatic acid
anhydrides in the presence of sodium or potassium salt of the acid corresponding to the anhydride, to
yields - unsaturated aromatic acids.
(i) CH3 COONa,
C6H5 – CHO + CH – C – O – C – CH 
3  C6H5– CH = CH – COOH + CH3COOH
3
|| || (ii) H /H2O,
O O
Mechanism
CH3 C O–
||
O 
CH3– C – O – C – CH3 CH3– C – O – C – CH3
|| || CH3 COOH || ||
O O O O
Ph–C – H
||
O
CH3 C OH
||
O
Ph – CH – CH2 – C – O – C – CH3 Ph – CH – CH2 – C – O – C – CH3
| || || | || ||
OH O O O O O
CH3 C OH
|| H+/ H2O
O

Ph – CH – CH2 – C – OH Ph – CH = CH – COOH
| || H2 O
OH O
- Hydroxy acid
(i)(CH CH CO) O / CH  CH  COONa,

Q.1 H 3C CHO 
3 2 2

3 2
A
(ii) H /H2 O,
OH (i)(CH CO) O / CH COONa, (i)(CH CO) O / CH COONa, 

Q.2 
3 2

3
 B 
C Q.3 
3 2

3
D
(ii) H3 O ,  CHO (ii)H /H2O, 
CHO O
O
||
H2C – C
(i) Sodium Succinate, 
Q.4 C6H5– C – H | O +  
 E
|| (ii)H3 O , 
H2C – C
O ||
O
O
CH– COOH
(i) MeCOONa
C
(ii) H3OO
+,  C
Q.5 O +F O
C
C
O O
Phthalylacetic acid
O
O
CH3 COO O MeCOO 
Q.6 O  G Q.7  H
(MeCO)2 O (MeCO)2 O
O2N
O O
O
|| (i) COONa
O
|| Me– CH – C COONa
Q.8 Ph – C – H+ | O (ii) H O,
3 
I
Me– CH – C
||
O
211
CHEMISTRY
Std. 11th &12th REFORMATSKY REACTION DPP 63
Reformatsy Reaction :
- halo esters when treated with Zn in gives organometallic halo ester which provides the attacking
Nu for the another reactant, which is a carbonyl compound. When Nu attacks on carbonyl compound
it gives an intermediate which upon acidic hydrolysis followed by heating, results in formation of -
unsaturated acid. The overall reaction is known as Reformatsky reaction.
O
||
Zn
Ph – CHO + CH2 – C – OEt 

Ph – CH = CH – COOH
| H3O / 
Br
Benzaldehyde
O O
+
|| O ZnBr
CH2– COOEt Ph–CH
Zn
Ph – CH – CH2– COOEt
CH2– COOEt  |
| O
+
ZnBr H3 O
Br
Br OH
EtOH + Zn + Ph – CH – CH2 – COOH
OH
/–H2O
Ph – CH = CH – COOH
Cinnanic acid
(1) Zn
Q.1 C6H5COCH3 + BrCH2COOEt  
A
(2) H3 O / 
O
(1) Zn
(2)PhCHO
Q.2 OEt  
B
(3) H3 O / 
Br
Ph O OEt (1) Zn/Ether
Q.3 + CH3CHO 

 C
(2) H3 O / 
Br
(1) Zn Se
Q.4 + BrCH2COOEt  

D  E
(2) H3 O 
- tetralone
Br
|
(i)Zn /Et 2O Se
Q.5 Eto – C – CH – CH 2CH 2CH 2 – CH 2  CHO  F  G
|| (ii)H3 O 
COOPh
Br
(i) Zn /Et 2O
Q.6  H
(ii) CH2O
(iii) H3 O ,
(i) Zn BrCHCH  CH  COOCH3 1. SOCl2 1. Zn  BrCH2COOEt LiAlH4

Q.7   I   J   K 
  L
(ii) H3 O (iii)., H2 O 2. CH3Li 2. H3O 3., H2 O
-lonone
212
CHEMISTRY
Std. 11th &12th CLAISEN CONDENSATION DPP 64
Claisen Condensation :
Esters undergo SNAE Reaction, when attacked by a generated by the interaction of a base (usually base
related to the Alkoxy anion of ester) with one of the molecule of ester and this attacks on another
molecule. The reaction over all is considered as condensation of esters known as claisen ester
condensation.
O O O
RONa Me – C – CH2 – C – OR
2 Me –C – OR 
A - keto ester
O O
O
 Me –C – OR
RO
CH3 –C – OR 
 CH 2 – COOR Me – C – CH2 – COOR
 ROH RDS
Nu OR
–R – O
O
Me – C – CH2 – COOR
Some times, when two ester groups are present within the molecule then the condensation occurs
intramolecule then cyclization caused thus is known as Dieckmann cyclization or Dieckmann's
condensation.
EtOK MeOK
Q.1 MeCOOEt  A Q.2 EtCOOMe  B
MeOK
Q.3 MeCOOEt + EtCOOMe   C
C2H5 ONa
Q.4 C6H5COOC2H5 + CH3COOC2H5   D + D
Ethyl benzoate
COOC2H 5
C2H5 ONa
Q.5 + C6H5CH2COOC2H5  E
COOC2H 5
COOPh
PhONa
Q.6 PhOOC   F
Q.7 Piperidone derivative

CH2CH2COOR 
C2H5 ONa H3 O
C2H5 – N   G   H

CH2CH2COOR
O OEt
OEt NaOEt
Q.8 O
OEt EtOH

O
COOEt
COOEt
NaOEt H3OO
+
Q.9  J K

COOEt
COOC2H5 COOC2H5
C2H5 ONa H3OO
+
Q.10 +  L M
COOC2H5 COOC2H5 
Diethyl-, -dimethyl
glutrate
213
CHEMISTRY
Std. 11th &12th KNOEVENAGEL REACTION DPP 65
KNOEVENAGEL REACTION :
Reaction of active methylene group with aldehyde and ketones is known as Knoevenagel reaction.
Z

Pyridine (i) H2O / H
RCHO + CH2   RCH = C(COOR)2  R – CH = CH – COOH
or piperidine (ii) , CO2
Z
Z can be
O
||
CHO, COOMe, COOH, CN, NO2, C – R ,SOR, SO2R, SO2OR etc.
Mechanism
 
  H C(COOR)
R 3N R3 NH  HC(COOR)2
2 2
O O O
+ OH
|| | R3NH |
R –C + CH (COOR)2 R –C – CH (COOR)2 R –C – CH (COOR)2 H2O
| | |
 
–R3N••
H H H

(i) H2O / H
R –CH = C (COOR)2  R – CH = CHCOOH
(ii) , CO2
High reactivity of the methylene group of the active methylene compound prevents
self-condensation of the aldehyde.
(1) Pip
Q.1 CH3CHO + H2C (COOR)2  A
(2) H O /  3
(1) Pip
Q.2 C6H5CHO + H2C(COOR)2  B
(2) H O /  3
(1) Pip
Q.3 HOOC–CHO + H2C (COOR)2  
C
(2) H3O / 
Glyoxalic acid
O
O || O
|| C– Me ||
Et 2NH nC5H11NH2
Q.4 Ph – C – H + CH2  D Q.5 Ph – C – H + CH3 – NO2  E
 
C– OEt
||
O
O
Me || O
CN CN ||
CH3 C– NH2 NaOEt
Q.6 C = O + CH2 F Q.7 CH2 + Ph – C – H  G
Me CH3COOH,  
COOR NO2
214
CHEMISTRY
Std. 11th &12th CARBENE DPP 66
1. Give product of the following reaction :
CHCl
3
  CHBr2 Cl
(1) KOH, 
(2)    
KOH, 
O O 2CH I
(3) 
 (4)  22
CHN2 Zn / Cu
O
(Intra molecular reaction)
OH
OH
OMe (i) CHCl  NaOH (i) CHCl  NaOH
    3 
     3 

(5) (6)
(ii) H (ii) H
Me
OH
(i) CHCl  NaOH
    3 
 CHI ClBr
(7) (8)    
(ii) H KOH
NH2
KOH 
(9) + CHCl3 + KOH  (10) R – NH2  x  R – N  C
OH
(11) (1) CO2 Ac2O

(A) (B)
(2) H (drug)
215
CHEMISTRY
Std. 11th &12th AROMATIC COMPOUND DPP 67
S.No. Compound Activating De-activating O/P Director Meta-director Rate of EAS is greater
group group than benzene
1.
2.
3.
4.
5.
6.
7.
8.
216
S.No. Compound Activating De-activating O/P Director Meta-director Rate of EAS is greater
9.
10.
11.
12.
13.
14.
15.
217
CHEMISTRY
Std. 11th &12th AROMATIC COMPOUND DPP 68
S.No. Compare Rate of EAS
1.
2.
3.
4.
5. , ,
6. , ,
7. , ,
218
CHEMISTRY
Std. 11th &12th AROMATIC COMOPOUNDS DPP 69
1. For each of the following compounds, indicate the ring carbon that would be nitrated if the
compound were treated with HNO3/H2SO4
a. f.
b. g.
h.
c.
i.
d.
j.
e.
k.
2. Give the product(s) obtained from the reaction of each of the following compounds with
Br2/FeBr3 :
O
(a) C–O (b)
(c) (d)
219
CHEMISTRY
Std. 11th &12th AROMATIC COMOPOUNDS DPP 70
1. What product is formed when benzene is treated with each organic halide in the presence of AlCl3 ?
(a) (CH3)2CHCl (b) (c)
2. What acid chloride would be needed to prepare each of the following ketones from benzene using a Friedel-
Crafts acylation ?
(a) (b) (c)
3. Which halides are unreactive in a Friedel-Crafts alkylation reaction ?
(a) (b) (c) (d)
4. Draw the product of each reaction.
H2SO 4 H2SO 4
(a) +   (b)  
H2SO 4
(c) (d)  
5. Draw the products formed when each compound is treated with HNO3 and H2SO4.
(a) (b) (c) (d)
220
6. Draw the products of each reaction.
HNO3
(a) (b)  

H2SO4
CH3CH2Cl
(c)    (d)
AlCl3
(e) (f)
SO3H
Br OCH3
SO3
(g) (h)
H2SO4
SO3H SO3H
7. Write out two different routes to ketone A using a Friedel-Crafts acylation.
8. Draw the products of each reaction.
HNO3 Br2
(a) CH3 C(CH3)3  
 (b) 
H2SO 4 hv
NO2
Br2
(c) HNO
3 (d) 
 
 FeBr3
H2SO 4
HNO
3 Br2
(e)  
 (f) 
H2SO 4 FeBr3
221
1. 1, 0, I, 1 2. 1, 0, I, 1 3. 2, 1, I, 2 4. 3, 2, I, 3
5. 3, 2, III, 3 6. 4, 3, I, 4

(1) HOH  
(2) MeOH  
(3) Phenol  
(4) Acetic acid  
(5) NH3  
(6) R – NH2  
(7) acetone  
(8) DMSO  
(9) DMF  
(10) DMA  
(11) HMPT  
(12) THF  
(13) DIOXANE  
(14) CCl4  
(15)  
(16)  
(17) CH3 – NH2  
O
O O
(18)  
[9]crown[3]ether
(19) Me2S  
O
(20) C – OH  
222
(21)  
Benzene
(22) H–F  
(23) Et – O – Et  
O O
O O
(24)  
[12]crown[4]ether
Answers Key of DPP No.-3

OH OH
OH OH
| |
1. (a) (b)
<
OH OH
OH
| OH
|
(c)
< (d) |
OH < OH (e)
>
C
|
2. (A) (B) (C) (D) C – C = C – C
3. (a) CHO (b) (c) (d)
(e) (f) (g) (h) +
Me Me
(i) (j) (k)
223
(l) (m) (n) (o)
CD3
D Cl
D
(p) (q) D (r) (s)
4. Consider mechanism.

1. a, b, e, g, h, i, j, k, m, n, o, p, q, r, s, t 2. B 3. A
4. 8 + 10 + 10 = 28 5. 3, 1, 3, 2 6. A 7. 7 + 8 + 7 + 10
8. 12 + 9 + 12 9. D

Ph Ph
CH3
CH3 CH3
H+ CH3 C C Et Ph C CH2 H+ Ph C CH
1. Et C C Et 2.
∆ ∆
OH OH O Et OH OH H O
H CH 3
OH OH OH OH
O H O C C CH 3
H H CH3 CH 3
+ +
H H
3. 4.
∆ ∆
H H
CH 3 O C C
H+ CH 3O CH2 C
5.
OH OH
∆ O
OH OH OH OH
O
+
  H → 5 2+ 3
6.
∆ 2 1
4 3 5 4
224
OH O
OH OH OH
6
+
+ +
  H →
5 2
2 1 6 1
7.
∆ 4
3
5 3
4
1. DIAZOTISATION REACTION
O
C CH2
OH NH2 OH
CH CH O CH   NaNO
  2 → CH
+
CH O
CH   →
3
Hcl 3
OCH3
NH2 +
NaNO
2.      2→
OH
Hcl OH
O
NH2 OH OH OH
O
NaNO2 +
3.   Hcl
  → 1 2 5 + 2 3
3 4 5 4
OH
+
CH3 CH CH
OH NH2
NaNO2
4. CH 3 CH CH      →
Hcl
  SbCl
  5→  
CH Migrate
     → 3
∆ ∆
5. +
Cl OH OH O
225
OH OH O
Br +
  AlBr
  → 3
6.
∆
 
Agl →
+ O
∆
7.
OH
I OH
OH OH OH O
6 +
 
Aq.AgNO
     → 3
2 3
∆
8. 5 2 +
6 4
I
4 3
5
1. Rate stability of carbon
(a)
> > >
CH=CH2 CH=CH2 CH=CH2 CH=CH2
CH=CH2
(b) > > > >

NH2 OCH3 CN NO2
(c) > > > > CCO4(-I)
(d) II > I
1. CH 2  CH 2  Hl 
 CH 3  CH 2 I 2. CH 2  CH 2  KBr 
HI
3.
KBr
6. +HI 

I
226

7. HCl
  8.
O o Cl HI 

I
I
H H2
HC(Ph) 2 C C CH2
H HC(Ph) 2 C C CH3
9. HI 

Me
Me
10. H 11.
C CH Ph 
HBr  CH C Ph HCl Cl

Br
+
1
Br
2 +
+ 1
12. 2 3
5 3
5 4
4
Cl
13. HCl CH 3 CH
CH2 CH Cl 
Cl
CH ≡ CH + HCl   → CH 2 = CH − Cl   →
HCl
CH 3 − CH − Cl
14.
|
Cl
Cl
15. HCl
CH 3 C CH CH 3 C CH2 CH 3 C CH3
2Eq
O Cl
227
16. HCl
Cl
dilH 2SO 4 OH
17. 18. H+/H2O
OH
H+1R-OH
H+/H2O
19. 20. OH
RO
Me Me
HCl
H D H D
21.
CH=CH2 CH-CH3
Cl
D +/D 2O
22. OD
+
OH 1 OPh
+ + +
H / 2
2
1
3 Ph-OH
23.
5 3 5 4
4
HBr
+ HCl
CH C CH2 CH CH2 CH C CH 2 CH CH 3
24. Br Br 25.
Cl
(KCP) (TCP)
228
HCl CH3 O
CH C CH CH2 CH2 C CH CH2 H+
26. 27. OH CH 2 CH 2 CH2 CH CH2
MeOH
Cl
3 1
4 2
CH2 CH CH CH CH2 H+/MeOH CH 2 CH C CH 2 CH3 H+
28. 29.
OH O 5 6 OH O

H3C OCH3 OCH3 OH
1. (i) (ii) (iii)
OH
COCH3
O
(iv) (v) (vi)
i Hg(OAc )2, H2O

       i Hg(OAc )2, EtOH
2. (i) –
O (ii)       
ii NaBH4, O H –
O
ii NaBH4, O H
i Hg(OAc )2, H2O
(iii)       
–
O
ii NaBH4, O H
i Hg(OAc )2, MeOH
(iv)        
–
O
ii NaBH4, O H
229
1. (i) CH3CH2OH (ii)
OH CH3
CH3
(iii) CH3 , H (iv) ,
H OH
CH3
CH2CHO
(v) CH 3  CH  CH 2 , CH3  CH  CH 2 , CH3  CH  CH 2 (vi)

| | | | | |
D H H D T D
HO OH
(vii) (viii) (ix)
HO
(x) (xi) (xii)
(xiii) (xiv) (xv)
2. (A) (B)
(C) (D)
Et Et
3. (A) (B) H
H
OH OH
230
H H H
(C) H (D) OH
OH
OH OH
4. (A) (B) (C)
5. (A) (single) (B) +
6. (A) (B)
(I) (II)
7. (A) (B)

CH3 CH3 CH3
CH3
1. * , Racemic mixture 2. * , Racemic mixture
OH OH
CH3 CH2CH3 CH2CH3
CH3
3. * , Racemic mixture 4. * , Racemic mixture
OH OH
CH3
OH *
OH OH O
5. 6. * 7. 8. CH 3 – C – CH 2 – CH 3
CH3 CH3 – CH – CH3
4-Products
OH OH
*
OH Ph – CH – CH2 – CH3 * *
9. 10. * 11. 12.
OH
2-racemic
2-dia 4-Products
231
CH3
OH OH CH3
* OH
HO * * OH
13. 14. 15.
3 alcohols (A) (B)
racemic Diastereomers
Br
16.

1. D 2. B 3. C 4. A 5. B 6. A 7. B
8. B 9. A,B,D 10. B 11. B 12. B 13. D 14. A
+
15. A 16. (a) (1) B2H6 / CH3COOD (b) B2D6 / CH3COOH (c) H2O/H

1. Racemic mixture 2. Meso 3. Racemic mixture
Br
4. Racemic mixture 5. + M.I. (racemic mixture)
Br
Br Br
6. Br + M.I. (racemic mixture) 7. CH3 – CH – CH2 (racemic mixture)
*
Br
Br
8. Meso 9. (single product) 10. Racemic mixture
Br
Br Br
CH2 – CH – CH2 – C  CH
11. *
(2 products)
Br
CH3 CH3
OH H Br H Br
12. + M.I. (racemic mixture) 13. H Br Br H (Diastereomers)
2 products
Br H H Br
CH3 CH3
CH3 CH3
H Br H Br
H Br Br H (Diastereomers)
14. 2 products
H Br Br H
CH3 CH3
232
Br Br
Br Br
15. 16.
Br Br
Br Br
(2 products)
(2 products)
Br Br
(2 products)
17. 18.
Br Br
Br Br (2 products)
19.
Br Br

Identify nucleophilicity order in the following :
1. I > Br > Cl > F 2. I < Br < Cl < F 3. HO – > H2O
.. –
4. NH 2– > NH 3
5. HO – < NH 2
6. H2O < NH3
7. CH3O > CN 8. HO – > CH3COO – 9. HO – < SH –

10. (CH3)3N < (CH3)3P 11. H2O < H2S 12. CH 3COO – < CH O –3
CH3
–
13. CH3OH > CH3 – C – OH 14. O < –
O
CH3
.. .. ..
N N N N
15. > 16. >
17. Leaving group order.
(a) I > Br > Cl > F (b) I > Br > Cl > F
233
O O
|| ||
(c) CH3–S–O > CH3 – C – O
||
O
O
|| CH3 – O
(d) CH3 – C – O >
O O
|| ||
(e) CH3 –S – O < CF3 –S – O
|| ||
O O
O O
|| ||
(f) < NO 2 S–O
CH3 S–O
|| ||
O O
O
O ||
(g) || < CF3 – S – O
CH3 S–O ||
|| O
O
(h) N2 > HO
..
(i). HO < H2O
..
(j) OH < Cl
(k) –OTs < –OBs
(l) HO > CH3
18. (I) C (II) B (III) C (IV) A (V) B

19. (I) C (II) B (III) B

1. A 2. B 3. B 4. B 5. A 6. B 7. B
8. B 9. B 10. A 11. B 12. A 13. B 14. Same

1. B 2. B 3. B 4. A 5. B 6. B 7. A
8. A 9. B 10. A 11. B 12. A 13. B 14. B
234
SN2 SN1
Cl Cl Cl Cl
1. > >
Cl Cl Cl Cl
2. > >
Br Cl Br Cl
3. > >
Br Br
4. Br > > Br
Cl Cl Cl Cl
5. > >
CH2Br CH2Br CH2– Br CH2Br

6. > >
Br > Br >
7.
Br Br
8. Br > Br Br > Br
O O
9. Br > Br Br < Br
10. O Br > Br O Br > Br
235
Br Br
11. >
Br > Br
> >
12. Cl Cl
Cl Cl

NaI
Br I
1. CH3COCH3
SN2
NaCN
2. CH3 – CH2 – CH2 – CH2 – CH2 – Cl CH3 – CH2 – CH2 – CH2 – CH2 – CN
DMSO
SN2
NaN3
3. CH2 – CH3 – CH2 – CH2 – CH2 – CH2 – Cl Ethanol CH2 – CH3 – CH2 – CH2 – CH2 – CH2 – N3
SN2
CH3 CH3
CH3 – C – Br EtOH CH3 – C – OEt
4.
CH3 SN1 CH3
5. Sec butyl bromide  2 - butanol

H O 2
SN1
CH2– Cl  CH 2–SPh.
6. Ph S Na
SN2
7. CH3 – I   CH3 – OH

aq. KOH
SN 2
236
8. Br EtOH OH
SN1
KSH
9.
Br acetone SH
SN2
Ph Ph
Ph – C – Br EtOH Ph – C – OEt
10.
Ph Ph
HI
1. CH 3 — CH 2 — CH 2 — OH CH 3 — CH 2 — CH 2 — I + H 2 O
∆
OH Br
2. + HBr  + H2O
3. CH3CH2CH2CH2OH + PBr3 Br + H
OH Cl
SOCl2
4. Pyridin
OH Cl
1.P-toluenesulfonyl chloride
5.
2. O
6. OH + H C l C l + H 2O
7. + HBr
OH Br
237
OH Br
8. 
+ HBr
OH xHI I
9. + I2
OH I
∆
10. (1) R — OH + HBr  → R + Br + H 2 O
∆
(II) R — OH + HI  → R – I + H2O
∆
(III) R — OH + HCl  → R – Cl + H 2 O
(IV) R — OH + PBr3  
Pyridin
 → R – Br + H3PO3
(V) R — OH + PCl3  
Pyridin
 → R – Cl + H3PO3
(VI) R — OH + SOCl2  
Pyridin
 → RCl + H3PO3
11.
OH
+ +
O H3O O O
OH OH
OH O
OH + O + +
OH
12.
238
O H 3O + O
O
O
H
OH + O +
O O
H
OH
H3O+ O
O + O
13.
O + OH –
+ +
OH O
OEt H3O+ O
14. OEt + 2 Et—OH
O
OH H3O+ O H3O+ OH
15. OEt + Et—OH 16. 2
OH
O
17.
O H 3O + O O O
+ + OH
O CH3 O CH3 O CH3 OH CH
3
H H
H
HO
OH O+
+ OH OH
HCHO + OH
OH + OH CH
CH3 3
239
HI
19. CH 3 − CH 2 − O − CH 3 CH 3CH 2 OH + CH 3 I  → CH 3CH 2 I + H 2 O
Excess
HI
20. CH 3OCH 2 CH 2 CH 3 CH 3OH + CH 3CH 2 CH 2 I  → CH 3 I + H 2 O
∆
HI
21.
CH3 CH CH2OCH3 I +CH 3OH CH3I+H 2O

CH3
HI
CH2OCH2CH2CH3 Ph—CH2—I +CH3CH 2CH2—OH

HI 
22.
CH3CH2CH2—I+H2O
NaOH
Ph — OH + Et — Br PhOEt  →
23. conc
Ph — O − Et Ph — OH + Et — I
HI
O—CH3 xHI OH HI I
24.. + 2 CH3I
O—CH3 OH I –I2
O Br
25.
H2 HBr OH
C CH3 +
CH3

H3C C OCH 2 CH3 + HBr Br + OH
26.
CH3
240
O O I– O
27. (a) + HI
+
I
OH
H2
(b) H2
C O + HI Ph C I+
CH 3 CH 3
CH 3 — CH 2 — CH 2 — O — CH 2 — CH 3 + HI  → CH 3 — CH 2 — CH 2 — OH — CH 3 — CH 2 — C — I
(c)
CH 3 CH 3
OCH3 + OCH3 I
+ HI HI I–
(d) (e) OC
O OH I H3
(f) + HI
OH I
O
Q. (1) R – Cl (2) Ph – CH2 – Cl (3) 2CH3 – Cl (4)
(5) (6) (7) (8)
(9) (10) CH3 C  N (11) (12)
(13) (14)

1. B 2. A 3. B 4. C 5. D 6. D 7. C
8. D 9. D 10. A
241
11. (A) OK , (B) OK , (C) OTs

O
18
1. CH3OH + PhOH 2. No reaction 3. + CH3OH
OH
OH
OH
4. PhOH + 5. + CH3OH 6.
H O OH
OH
OH
7. 8. Ph–OH + OH–CH2–CH2–CH2–CH–OH + EtOH
HO
CH3
OH HO
9. 10. 11.
HO OH
OH OH
OH
12. PhOH + EtOH 13. + CH3CHO 14. CH3CHO + CH3–COCH3
15. Ph – OH + CH3CHO

1. CH3OH + I and (CH3)3 C – I + CH3I 2. EtOH + CH3I and CH3I + EtI
3. CH3I + PhOH and CH3I + PhOH 4. PhCH2I + EtOH and PhCH2I + EtI
5. No reaction 6. No reaction
7. CH3I + CH3CH(OH)CH3 and CH3I + CH3CH(I)CH3 8. CH3CH2I + H2O and CH3CH2I
+ H2O
9. No reaction
OH I
10. CH3CH2I + and + EtI
OH I
11. I + and I +
12. Ph I + PhOH and Ph I + PhOH

13. EtI + PhOH and EtI + PhOH
14. Ph I + EtOH and Ph I + EtI
15. I OH and I I
+ +
242
1. 1 2. 1 3. 1 4. 2 5. 1 6. 3 7. 2
8. 1 9. 2 10. 2 11. 2 12. 2

1. 9 + 9 + 11 + 6 = 35 3. 4 + 7 + 8 + 8 = 27 5. 8 + 8 + 4 = 20
6. 6 + 5 + 8 = 19 7. 7 + 8 + 8 = 23

1. (a) (i) > (ii) (b) (i) > (ii) (c) (i) > (ii) (d) (i) > (ii)
(e) (i) > (ii) (f) (i) < (ii) (g) (i) < (ii)
2. (a) (b) (c)
3. (a) (b) No reaction (c) (d) (e)
4. (a) (b) (c) (d) (e)
(f)
5. (E2 is anti-elimination)
6. (a) (b)
7. Bromine at equotorial
8. (a) Base abstract -hydrogen which has less no. of -hydrogen (Zaitsev - rule)
(b) Steric hindrance

(A) Excluding Stereo Including Stereo (B) Excluding Stereo Including Stereo
1. 1 1 1. 2 3
2. 2 3 2. 3 3
3. 2 2 3. 5 6
4. 2 4 4. 2 2
5. 3 4 5. 2 3
6. 3 5 6. 2 3
243
7. 3 4
8. 1 1
Answer of DPP No. - 26

1. (1) OH (2) (3) Cl
OH
(racemic)
(4) (5) (6)

Cl
(racemic) cis trans
C
2. (a) H N N (b) SN2
CH3CH2CH2
3. Diazotic acid
CH3 CH3
4. (1) (2) (3)
H3C
CH3
(4) (5) H2C = CH – CH3 (6)

N
H3C CH3
(7) (8) (9) (10)

N

1. (A) PhCH2OH (B) Ph – OH (C) PhCH2I
2. (A) EtOH (B) EtOH (C) EtI
Br OH Cl
3. (A) (B) 4. (A) (B) (C)
5. 6.
I OH
Cl C CNa
7. (A) (B) 8. (A) (B) 9.
244
Cl
|
10. (A) CH3 – C = CH2 (B) CH3 – C  CH (C) CH3 – C  CNa (D) CH3 – C  C – CH3
11. (A) CH2 = CH – Cl (B) CH  CH (C) Na – C  CNa (D) Et – C  C – Et

1. x  3, y  1 2. x  4, y  2 3. x  6, y  2
1. (a) 2, 1, 3, 3 (b) 3, 1, 3, 1 (c) 1, 1, 0, 0 (d) 2, 1, 1, 1
(e) 3, 1, 3, 1 (f) 3, 1, 4, 3
2. (a) 0+2=2 (b) 3+3=6 (c) 4+3=7 (d) 0 (e) 4 + 2 = 6

1. (a) 2+4=6 (b) 4 + 6 = 10 (c) 2+5=7
2. (P) 1, 2, 3, 4 (Q) 1, 2, 3, 4 (R) 1, 2 (D) 1, 3, 4
Answer Key of DPP No. - 30
Na
1. CH3 CH2 Cl
DE
Al-Hg
CH2Br
OH
4 Na C2H5OH OH
2.(1) 2.(2)
Br O
I Cu
I
+ 120–260oC
3.
I
I
Cl
Na
4.
DE
245
Br
Na
5.
DE
Cl 14 14
6.
Na
14
DE
Br
Na
7. DE
Br
Cl Na
8.
DE
Na
9. .
DE
Br
Na
CH3 Cl CH3 CH3
1.
Ether
Na
Et Cl H3C CH2 CH2 CH3
2.
Ether
Na
3. CH 3 − Cl + CH 3CH 2 − Cl CH 3 − CH 3 + CH 3 − CH 2 − CH 2 − CH 3 + CH 3 − CH 2 − CH 3
Ether
Ph Ph
Na Na
(Ph)3C–I (Ph) 3 C C Ph
4. Ether 5. I
Ether
Ph Ph
246
Na
6. Cl Br 7.
Ether
Cl Na
Na
8. 9.
Ether Ether
Cl Cl Br
Na Na
10. Cl Cl 11.
Cl
Ether Cl
Ether
Na
12. Ph — Cl Ph — Ph
THF
Na
13. Ph — Cl + CH 3 — Cl Ph — CH 3 + CH 3 — CH 3 + Ph — Ph
THF
Cl Na CH2 CH2 Na
14. 15. CH2 CH2 + ZnBr2
Ether Zn
Cl Br Br
Cl
6 Ag/Poweler
16. H C Cl H C C H + 6 AgCl
Cl
CH2 C C CH 2 Na
H H
17. Ether
Br Br
Na
Ether
18.
Br
247
Electrolysis
1. CH 3COOK CH 3 — CH 3 + CO 2 ↑ + H 2 ↑
NaOH
Electrolysis
2. Et — CH 3 — CH 2 — CH 2 — CH 3 + CO 2 + H 2 ↑
NaOH
COOH Electrolysis
3. + 2 CO 2 + H 2 ↑
HOOC NaOH
COOH
Electrolysis
4. | | | + 2CO 2 + H 2 O ↑
NaOH
COOH
COOH
Electrolysis
5. | | | + 2CO 2 + H 2 O ↑
NaOH
HOOC
N a O O C
Electrolysis
6.
C O O N a
     →
NaOOC Electrolysis
7.
COONa      →
SO3K Electrolysis
8. SO3K      →
COOH Electrolysis
9. +
SO3H NaOH
COOH
NaOH
10.
Electrolysis
+
COOH
SO3H
NaOH
11.
Electrolysis
+
SO 3H
248
KO 3S
C C Electrolysis H 2 C = C = C = CH 2
SO3K      →
12.
CH 2-I
1.   Na  →
 Dryether Ph — CH — CH — Ph 2 2
Br Br
2.   Na  →
 Dryether
+
Br
CH 2 CH 2-Br
3.   Na  →
 Dryether
Br
4.   Na  →
 Dryether  Se
 →
Br
Br
5.   Na  →
 Dryether +
Br
Br
6.   Na  →
 Dryether
Br
249
* Na * * *
C H 2 = CH — CH 2 — Cl C H = CH — CH 2 — CH 2 — CH = C H 2 + C H 2 = C =
DE
8. * *
C H 2 + CH 2 = CH – C H 2 – C H 2 – CH = CH 2
Br
Cl
9.   Na  →
 Dryether 10.   Na  →
 Dryether
Cl
Cl
11.   Na  →
 Dryether
Cl CH2-CH3
12. CH 3CH 2 — Cl +   Na  →
 Dryether + CH 2 = CH 2 +
13.
Number of Number of monocholor product

Monochlor product chloro product
(excludng stereosiomer)
(1) 4 3
(2) 3 2
(3) 6 4
250
(4) 10 6
(5) 6 4
(6) 1 1
(7) 1 1
(8) 1 1
(9) CH2 2 2
1. (1) (2) (3) (4)
OH
OH Ph Ph OH
(5) (6) (7) (8)
Ph Ph Ph Ph
OH
Ph OH CH3
(9) (10) (11)
OH
(12) (13)
HO
251
2. (a) x=5 (b) 4 (c) 5

H OH H OH
(a)
Ph HO
r 1 > r2 > r3
H OH
(b) CH3CH2OH, r 1 > r2
H OH
(c) r3 > r 1 > r 2

NO2
Ph
(d) r1 > r2 > r3
HO H HO Ph
HO Ph
OH OH Ph
(e) r1 > r 2 > r 3 > r 4
H Ph
OH
(f) Ph No reaction r1 > r2 > r3
Ph OH
OH Ph OH Ph O OH Ph
(1) (2) (3) + (4)
Ph Ph Ph Ph Ph Ph Ph Ph
OH Ph O
(5) (6) (7)
Ph Ph Ph Ph
(8) Ph – CH3 (9) Ph – Br
252
MgBr
EtMgBr
(a) ; H3O
O H3O
O
O
MgBr
H3O
MgBr
O MgBr
(b) H3O ; CHO
H3O
O O
CT3 MgBr CD3 MgBr
(c) CH3 CH3 ; CH3 CT3
H3O H3O
O
CH3MgBr
CD3 CT3
H3O
2. (a) 7 (b) 8
Answer Key of DPP - 39
(a) 3º alcohol (b) 3º alcohol (c) 3º alcohol (d) 3º alcohol (e) 3º alcohol (f) 3º alcohol (g) 3º alcohol
(h) 3º alcohol (i) ketone (j) 2º alcohol (k) 2º alcohol (l) 3º alcohol (m) 3º alcohol (n) alkane
(o) No reaction (p) 3º alcohol (q) 2º alcohol (r) No reaction (s) alkane (t) No reaction (u) 3º alcohol
(v) ketone (w) 3º alcohol (x) 3º alcohol (y) 3º alcohol (z) 2º alcohol
Answer of DPP-40
1. A 2. D 3. D 4. C 5. C 6. D 7. A
8. A 9. C 10. B 11. D
12. (A) R, (B) Q, (C) S, (D) S 13. Due to acidic hydrogen
14. (a) + CH4 + MgBr2 (b) CH2  C  CH2 (c)

| |
Ph Br OH
OH OH
15. (a) (b) (c) (d)
CH3
CH3
Answer of DPP-41
1. 4 2. 4 3. 5 4. 4 5. 2 6. 3 7. 3
253
8. 4
Answer of DPP-42
1. 8 2. 6 3. 7 4. 2 5. 2 6. 4 7. 7
8. 2 9. 4 10. 2
Answer of DPP-43
OH Ph Ph
Ph Br
1. (i)  
(A) (B) (C)

OH
Br
(ii) H  
(B) (major)
(A) Br
(minor)
OH Br
(iii) H H   major

(A) (B)
+
major
Br
minor
OH
CH3 O O
OH Et
(iv) (v)
(B) (C)
(A)
MgBr OH
O
OH || OH
(vi) (vii) Ph Ph H Ph – C – Ph (viii) |
Ph (C) Ph – CH – Ph
(A) (B)
OH
|
(ix) (x) C (xi) CH4
Benzene
OH
OH Ph
OH
2. (i) Et (ii) (iii) (Ph)3C – OH (iv) Ph OH
Et
254
OH OH OH
HO OH
(v) + (vi) (vii) (Ph)3 C – OH (viii)
Ph Ph Ph Ph Ph Ph Ph Ph
Ph
OH
(ix) + EtSH (x) (Ph)3 C – OH (xi) (Ph)3 C – OH
Ph
Ph
Answer of DPP No.-44

O H
H H ||
1. (i) O + O=C ] (ii) CH 3  C  H + H C=O
H H
CH3
H H
(iii) (iv) CH3 + C=O ]
O O O H
O O O O
(v) + (vi) H H]
O O H
H
(vii) C=O + O  C  CH 2  C  O + O  C  CH3 ]
H | | |
H H H
2. (i) or (ii) (iii)
(iv) H (v) (vi)
CH3 H
| H H
C = C – C = CH2
(vii) | (viii) (xi)
CH3
255
(x)
H (xi)
H O CH3 O H O
O CH3
C C C
3. (i) Only one (ii) + +
O C C
C H
CH3 O H O O
(iii)
4. (a) 1 (b) 3 (c) 6

1. Meso 2. Racemic mixture 3. Racemic mixture
OH OH
4. Racemic mixture 5. (Meso) 6. (Meso)

OH
OH
OH OH
7. CH3 – CH – CH2 , (racemic mixture) 8. Racemic mixture
*
9. Single product 10. Meso 11. Racemic mixture
CH3 CH3
H Br H Br
OH OH
, H OH + HO H
12. (racemic mixture) 13.
H OH HO H
OH OH
CH3 CH3
2 products, diastereomers
CH3 CH3 Br
Br Br
H Br H Br
Br Br Br
H OH + HO H
14. HO H H OH 15.
CH3 CH3 Br Br Br
Br Br Br
2 products, diastereomers
3 Products
Br Br H Br Br Br H Br
H Br H Br
16.
Br Br Br Br
Br Br Br Br
4 products
256
CH3 CH3 Br Br
Br2 H Br H Br * Br
17. , , , + M.I. ,
CCl4 H Br , Br H
(i) (ii) (iii) (iv) CH3 CH3 Br
Alkenes of C4H8 (i) (ii) (iii) (iv)
x=4: y=6:

1. 2, Enantiomer 2. 1, Meso 3. 1, Meso 4. 1, Meso
5. 2, Enantiomer 6. 2, Enantiomer 7. 2, Diastereomer
8. 2, Diastereomer 9. 2, Diastereomer 10. 2, Diastereomer

1. B 2. A 3. D 4. D 5. B 6. C 7. C
8. D 9. C 10. B 11. A 12. A 13. B 14. A
15. D

1. R – CHO + HCHO 2. R – CHO + RCHO 3. R2CO + RCHO
4. RCHO + HCOOH + RCHO 5. R – COOH + R – CHO 6. 2HCHO + CO2
7. R – COOH + R – CHO 8. 2HCHO + CO2
9. R – COOH + R – COOH 10. RCHO + RCHO + NH3 11. No reaction
12. 4HCOOH + HCHO + 4HIO3 13. 5HCOOH + HCHO + 5HIO3 14. 5HCOOH + HCHO + 5HlO3
15. 2HCHO + 3HCOOH + CO2
MeO – CH
16. 17.
CHO
O
CHO
HC
CHO + HCHO + HCO2H
18. (A) (C)
19. CH3 – (CH2 )7 – CO2H  HO2C – (CH2 )7 – COOH
20. (i) CH3 – CH3 (ii) CH3 – CH3 (iii) (iv) (v)
257
NH2 O
1. (a) (b) (c) OH (d) CH3CH2OH
H
OD
H
(e) No Reaction (f) NH2 (g) H
OH OH
O
H H ||
(h) H (i) D (j) (Me)2CHCH2CH2CH
OH
(k) N (l) (m)

N
CH3
OH OH
O
(n) (o) (p) + CH3OH
OH
OH OH
OH OH OH
OH
(q) (r) OH +
and
O
O OH
OEt OH OH SH
(s) OMe (t) (u) (v)
HO OH
OH D
(w) CH3OH (x) CH3CH2OH (y)
258
OH
1. 2. CH3–(CH2)14–CH2–OH 3. CH3–CH=CH–CH2–OH
4. CH2(NH2)CH2CH2–OH
5. (i) CH3–CH2–OH (ii) 2 CH3CH2–OH (iii) CH3–CH=CH–CH2–OH, C2H5–OH
OH
D
OH
6. 4CH3–CH2–CH–CH3 7. R–H 8. (i) Ph–CH–CH 3 (ii)
D
OH
OH
9. 10. Ph–CH–CH2–CH2
CH3–CH–CH2–COOC2H5
COOH
OH OH
11. CH3–CH–CH2–CH2–CH–CH3 12. CH2OH(CHOH)4CH2–OH
13. Ph–CH=CH–CH2–OH 14. NC–CH2–CH2–CH2–OH 15. R–CH2–OH
16. O2N CH2–OH
1. Meso 2. Racemic mixture 3. Racemic mixture

4. Racemic mixture 5. Meso 6. Meso
D D
7. CH3 – CH – CH2 , 2-productss 8. Single product (cis)
*
D D
D D
+
9. (Racemic mixture) 10.
DD DD Racemic mixture
H H H H
C=C C=C
CH3 CH3
11. CH3 Single product 12. H Single product
C=C C=C
H H H CH3
259
CH3
HC
(cis)
C Ph
H Ph
H CH3 H3C H
13. (Single product) 14. H CH3 , Meso 15. + M.I. (Racemic mixture)
H CH3
H Ph
Ph
C
C
H3C H
OH
CH3
1. PhCH2CH2CH2COOH 2. 3.
CH2CH3
4. Ph–CH2–CH3 5. 6. Ph – CH2CH3
NH2
7. 8. CH2–CH2–CH2–COOH
CH2
9. 10. 11. Me(–CH2)5–CH3 12.

O
Answer Key of DPP No.53
O O O
1. Wolf-kishner 2. 3. ,
260
CH2CH3 CH2CH3 OH
4. ; 5. 6.
CH3
Cl
OH

MeO CH3
(i) (ii) (iii) (iv)
MeO
(a) PhCOCH3 (b) Cyclohexanone (c) Acetone (d) Cyclohexanone

(e) Cyclohexanone
O
||
(f) PhCOCH3 (g) (h) (i)
HOOC H
(j) Acetone (k) Cyclohexanone (l) CH3 – COOH (m)

O
H
(n) (o) O (p) No reaction (Upto 300°C)
H
O

(a) 2 (b) 4 (c) 2 (d) 2 (e) 0 (f) 1
(g) 1 (h) 0 (i) 1

O
1. A – R ; B – T ; C – P,S ; D – Q 2. A 3. A,B 4.
OCH3
O
O O
CH3 ||
5. 18 6. C – OCH3 7.
O HO O
261
O O
O
O O
8. 9. 10.
O
R
R1
O
O H
–
OH + CH3 – CO2
11. O 12. 13.
F3C RO C – O – Et R2
Br COOH
18
O Ph O
Ph
14. O 15. + MeOH
(C) O
(A) (B)
O
OH
O – C – Ph
–
16. (a) (b) (c) Ph – CO 2
O
O OH OH
OH O CH3
1. (a) + 2CH3–OH (b) + 2CH3CH2–OH (c)
OH H OH H
O
O
(d) CH 3–COH+HO NO 2 (e)
2CH3–C–OH + HO-CH2CH2-OH
O
O
2. (a) + (b) OH
CH3–COH + NH2 +
NH3
O O
3. (a) (b)
CH 3–C–CH 3 CH 3–C–OCH 3
O O
4. (a) (b)
H–C–NH2 NH2–C–NH2
262
O
O O
C
OH OCH3 O NH CH3
5. (a) (b) (c)
CH3
O C OH
O
Cl O
O
(d) + (e) Cl NH (f)
N
H2N C O
O O
N NH2
(g) (h)
N

OH
|
1. (1) (A) CH 3  CH 2  CH  CH  C  H (B) CH 3  CH 2  CH  C  C  H
| || | ||
CH 3 O CH 3 O
O OH Ph
|
(2) (C) (3) (D) Ph  CH 2  CH  CH  C  H
| ||
OH O
O OH O
(4) (E) (F)
CH 3 CH 3
| |
(5) (G) Ph  C  CH 2  C  Ph (H) Ph  C  CH  C  Ph ]
| || ||
OH O O
263
O O
CH3 OH
2. (1) (A) (B) (2) (C) C—CH3
HO O
O O O
(3) (D) OH (4) (E) (F)

CH3 OH
CH3
(5) (G) ]
C—CH3
O
3. Excluding Stereo Including Stereo
(1) 4 12
(2) 2 4
(3) 4 6
(4) 6 16
(5) 4 12
OH
|
(1) Me  CH  CH 2  CHO = 2
*
* *
Me  CH  CH  CHO
| | = 4
OH CH 3
*
Et  CH  CH 2  CHO
| = 2
OH
* *
Et  CH  CH  CHO
| | = 4
OH CH 3
OH
|
(2) Ph  CH  CH 2  CHO = 2
*
OH
|
Me  CH  CH 2  CHO = 2
*
264
OH
|
(3) CH 3  CH  CH 2  CHO = 2
*
OH
|
CH 3  C  CH 2  CHO
| = 1
CH 3
OH
|
CH 3  C  CH 2  COCH 3
| = 1
CH 3
OH
|
CH 3  CH  CH 2  COCH3 = 2
*
OH
| *
(4) CH 3  CH  CH  COCH 3 = 4
* |
CH 3
OH
|
CH 3  CH  CH 2  CHO = 2
*
OH
| *
CH 3  C ——— CH  COCH 3 = 4
*| |
CH 2CH 3 CH 3
OH
|
CH 3  CH  CH 2  CO  CH 3 = 2
*
OH
|
CH 3  CH  CH 2  COCH 2 CH 3 = 2
*|
CH 2CH 3
OH
|
CH 3  C  CH 2  CHO
*| = 2
CH 2  CH 3
265
OH
|
*  COCH
Ph  CH  CH
(5) 3 = 4
* |
CH 3
OH
|
Ph  CH  CH 2  COCH 2CH 3 = 2
*
OH
|
Me  C  CH 2  CO  Et
|* = 2
Et
OH
| *
Me  C — CH – COCH 3
*| | = 4
Et CH 3
O
||
4. (1) (2) CH3  C  CH3
|| ||
O O
O
||
C–H
5. (1) (A) (B) C–H
||
CH2 – CH2 – C – H O
||
O
O
CH—C6H5 CH3 ||
(2) (3) A= B= CH3  C  H
O ||
O
O O O
|| || ||
(4) CH 3  C  CH 2  CH 2  C  CH 3 (5) CH 3  C  CH 2  CH 2  CH 2  CHO
6. (C)
1. D 2. B 3. D 4. A 5. A 6. B 7. C
266
8. D
O
O
9. (i) H O + H3C–OD 10.
D O + DCH2OD
O
OH O
| ||
11. (i) Ph–CH2OH + H O 12. Ph – CH – C – O
CH2OH
13. O2N–C–CH2OH
CH2OH
The compounds which give positive iodoform test are :

(1), (5), (7), (10), (13), (16), (20), (21), (23), (24), (25), (27), (28), (29), (30), (31), (32), (34), (37), (38) (39),
(41), (42), (43), (46), (47), (48), (49).
267
O O O

Q.1 CH3 C + CH–C C–CH2–CH3
O
H CH3

O O O
CH3 C CH–C
C– C–CH2–CH3
O
H CH3
+
H3O
OH O O
CH3 C CH–C–OH + CH3–CH2–C–OH
C–
H CH3
O
CH3 CH=C–C–OH + H2O
CH3
O O
••
CH2–C C–CH3
OH OH OH
O OH O
Q.2
C–H C–CH2–C–O–C–CH3 C–CH2–C=O + CH3–C–OH
O H O
–
O O OH H
(B)

OH
CH=CH–C–H
O
(C)
268
O
•• O O
Q.3 + CH2–C–O–C–CH3
H CH2–C C–CH3
O C O CH O
O –
O
+
H /H2O/
O O
O O
CH2–C C–CH3
CH=CH–C–OH + CH3–C–OH + H2O O CH O
O
OH
O
HO O C
Q.4 C––CH–C
C CH=C O
O
H CH2–C CH2––C
O (E) O
–
O O
O O O O
O O CH2–C C–CH3
C C O CH–C–OH + CH3–C–OH
Q.5 + C
O + CH3–C C–CH3  O H3O /
C O
O
O O
O
(F)
O O O O
O O C–CH2–C C–CH3
C ••

Q.6 O + CH2–C C–CH3  O
O=N O O=N C–OH
O
O O O
O O O
C–CH2–C C–CH3
Q.7 O
C–OH
O
–
O CH3 O
OH CH3 O
Ph–C–– C C
H3O
Q.8 O 
 Ph–CH–C–C–OH
H CH
C CH–C–OH
CH3 O O
CH3
269
–
O O O O OH O

Q.1 C6H5–C–CH3 + :CH2–C–OEt  C6H5–C–CH2–C–OEt  C6H5–C–CH2–C–OH
CH3 CH3
O
C6H5–C=CH–C–OH + H2O
CH3
O O –
O OH
H3O
Q.2 EtO–C + Ph–C–H  CH3–CH–C–H   CH3–CH–C–H  
 CH3–C=CH–Ph
CH
•• Ph Ph O=C–OH
 O=C–OEt O=C–OH 
  (B) 
–
O O O
Q.3 Ph–CH2–CH–C–OEt + CH3–C–H Ph–CH2–CH–C–H
••

C CH3
OEt
 O 
H3O+
OH
Ph–CH2–C=CH–CH3  Ph–CH2–CH–CH–CH3
COOH  COOH 
   
O
–
O O CH–COOH
CH2–C–OEt
••
Q.4 + CH2–C–OEt  
(D)
Se/
CH2–COOH CH–COOH
Tautomers
(E)
270
O
Q.5 EtO–C–CH–CH2–CH2–CH2–CH2–C–H
••

O
–
O
O O O O
C–H C–OEt
C–OEt C–OH C–OH C–OH
Se/ Se/
O
(F) (F)
OPh
OPh –
O=C O OH
O=C O=C
: O C–H CH2–OH
Q.6 + H–C–H
H
O
O
CH2–CH=CH–C–OCH3

:CH2–CH=CH–C–OCH3 –
Q.7 O O
(I)
H3O+/
O
O
SOCl2 C–OH
C–Cl
CH3H
–
O O O
O
C–CH3 –
CH2–C–OEt C–CH2–C–OEt
(J) CH3
O
CH–CH2–OH
C=CH–C–OH
C
CH3
CH3
271
O O
Q.1 CH3–C–CH2–C–OEt
(A)
O O
Q.2 CH3–CH2–C–CH–C–OMe
CH3
(B)
O O O O O O O O
Q.3 CH3–CH2–C–CH2–C–OEt + CH3–C–CH2–C–OEt + CH3–CH2–C–CH–C–OEt + CH3–C–CH–C–OEt
(C) (C) CH3 CH3
(C) (C)
O O O O
Q.4 C6H5–C–CH2–C–OEt + CH3–C–CH2–C–OEt
(D) (D)
O C 6H 5 O
Q.5 C–CH–––C–OEt
C
O OEt
(E)
OH O
O O
CH C–OPh
Q.6 C–CH2–CH2–CH2–CH2–C–OPh
••

PhO
(F)
O O
OR
O C C–OH
CH2–CH–C–OR CH2–CH CH2–CH
•• – H3O+
Q.7 C2H5–N  C2H5–N C=O +RO C2H5–N C=O
CH2–CH2–C–OR CH2–CH2 CH2–CH2
O
(G) (H)
CH2–CH2
CO2 + C2H5–N =O
272
O=C–OEt OEt
O=C
O
O
C–OEt
Q.8 C–OEt C–OEt
••
 O (I)
O
O
O
C–OEt COOH
C–OEt O
Q.9 C–OEt C
C=O C=O
O O
 C–OEt C–OEt C–OH C–OH
••
O O O
(J) (K)
O O
O C–OCt C–OH
O O
C H3O
Q.10 

C
O O
O C–OEt C–OH
O O
(L) (L) (M)
273
O O
–
O C–OR O C–OR COOH
+
 H3O /
Q.1 CH3–C + ••CH CH3–C–CH CH3–CH=C CH3–CH=CH–COOH
C–OR C–OR COOH
H H
O O
OH OH
COOR COOH
Q.2 C6H5–C–CH C6H5–C–CH C6H5–CH=CH–COOH
H3O+/
COOR COOH
H H
O
O OH O
C–OR +
Q.3 H3O /
C–C–CH C–CH=CH–COOH
HO C–OR HO
H
O
O O •• O
– Et–N–Et
O
C–Me C–Me H C–Me

Q.4 Ph–C–CH Ph–CH=C Ph–CH=C ••
C–OEt C–OEt C–N–Et
H
O O O Et
–
O O O O O

••
Q.5 Ph–C–H + CH2–N  Ph–C–CH2–N Ph–CH=CH–N
–
O H O O
(E)
–
O O
 CN CN CN
Q.6 C + ••CH  CH3–C–CH CH3–C=C
CH3 CH 3 C–OR C–OR C–OR
CH3 CH3
O O O
(F)
–
O O
 CN CN CN
Q.7 Ph–C–H + :CH Ph–C–CH Ph–CH=C
NO2 NO2 NO2
H
(G)
274
O O
Cl Br O
1. Cl 2. 3. 4.
Cl
OH
O O H
OH Cl
OMe
OH
H
5. 6. 7. 8.
O H Me
N=C
9. 10. X  CHCl3 11. (A) = Salicylic acid , (B) = Aspirin

S.No. Activating De-activating O/P Director Meta-director Rate of EAS is greater
1.  ×  × 
2.  ×  × 
3.  ×  × 
4. ×    × ×
5.  ×  × 
6.  ×  × 
7.  ×  × 
8. ×  ×  ×
9. ×   × ×
10. ×  ×  ×
11. ×   × ×
12. ×  ×  ×
13.  ×  × 
14.  ×  × 
15.  ×  × 

1. 4>3>1>2 2. 1>2>3 3. a>b>d>c
4. 3>1>2 5. 2>3>1 6. a>b>c 7. c>b>a
275
OH O
O ||
|| CCH3
NHCCH3
1. a. b. c.
Br
COOH
O CH3 Cl
||
OCCH3
d. e. f.
CH3OC Cl
||
O NO2
OH CH3 NO2
OH
g. h. i.
CH3
OCH3
SO3H
j. k.
Cl
O
C–O CH2O
2. (a) (b)
NO2
O O
H3C C COCH3
(c) (d)
CH3O
Answer of DPP No. -70
1. (a) (CH3)2CH — (b) (c)
276
2. (a) + (b) +
(c) +
3. (a), , (c)
4. (a) (b) (c) (d)
5. (a) (b) (c) (d)
6. (a) (b) (c) (d)
(e) (f)
(g) (h)
7. (1) (2)
8. (a) (b) (c)
(d) (e) (f)
277

12th Organic Chemistry (DPP)

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12th Organic Chemistry (DPP)

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Std.

12 Topic : Organic Chemistry (DPP)

Answers of DPP No. – 1

Answers of DPP No. – 21

Answers of DPP No. – 22

2. Which of following is 1° amine ?

3. Which of following is 3° amine ?

5. Number of 1°, 2° and 3° hydrogen in isooctane is:

(A) (B) (C) (D)

8. Which of the following compound contain only 2 types of carbon atom

(A) (B) N N (C) (D)

9. Which of the following is a 2° amine.

10. Classify the following alcohols as primary, secondary, or tertiary:

(c) (CH3)2C(OH)CH2CH3 (d)

11. Classify the following amines as primary, secondary, or tertiary:

(1) C4 H10 (2) C4H8

(3) C4H6 (4) C5H12O

(5) C5H10O (6) C5H8O

(7) C6H12 (8) C4H8Cl2

(9) C4H8Br2 (10) C4H10O

(11) C10H20 (12) CNH5

(13) C3H6O (14)

(25) CH3 – NH2 (26) C2H3N

3. Match the column :

10. 11. .. 12.

19. 20. 21. C9H16 NOCl

Number of Functional group in above compound is

5. The functional groups in Cortisone are : HOH2C

7. Present functional group is

(A) ketone (B) ester (C) ether (D) alcohol

2. Which of following is phenol ?

(A) (B) (C) (D)

(i) Which functional group is not present in above compound ?

6. CH2 = CH – CH2 OH CH2 = CH–OCH3

12. CH3OCH3 & CH3OCH2CH3

CHO CHO CH3

Compound P.O.S() C2 C3 COS

Q. How many compounds show geometrical isomerism ?

H3C H2C CH3

H3C H3C CH3

H2C CH2 H3C CH3

H3C CH2 H3C

(53) CH3 (54) (55)

(58) CH3 (59)

(63) (64) (65)

(66) (67) (68)

(69) (70) CH3 + O

(76) OH (77) (78) CH3 (79)

(90) (91) (92)

(107) (108) (109)

CH3 CH3 CH3 H

I amd II are not geometrical isomers of each other because

I and II are geometrical isomers of each other because

(A) (B) (C) (D)

(a) CH3–CH=CH–CH=N–OH (b) (c)

(d) CH3–(CH=CH)3 – Ph (e) (f) CH3–CC–CH=CH–CH3

7. Which of the following compound can show geometrical isomerism.

(A) (B) (C) (D)

8. The geometrical isomerism is shown by

(A) (B) (C) (D)

(A) (B) (C) (D) Me–N=N–Me

10. Assign E & Z configuration to following compounds.

(A) (B) (C) (D)