Alkyl and Aryl Halides 6.

Chapter 6 Alkyl & Aryl Halides

INTEXT EXERCISE: 1
1. Alkyl halide having maximum molecular wt. has 8. Fact.
highest boiling point.
9. Fact
2. BP: P > S > T as Branching increases surface area
decrease, Vander waal forces decreases hence
boiling point decreases. 10.

3. Fact
4. As molecular wt. increases density increases
5. Fact
6. Fact.
7. As length of parent chains changes hence chain
isomers.
INTEXT EXERCISE: 2
1. In hunsdiecker reaction as CO2 released hence No.
of carbon in product is less by 1 carbon atoms.
NaI
2. R-X R - I + Na X ppt .
]x & Cl as Brg Acetone

3. Fact

4. 6. Fact
7. reactivity: HI > HBr > HCl
Nu : - I > - Br > - Cl
8. reativity stability of carbocation.

5. 9. Incase of thionyl chloride all other products are gases

to it is easy to get pure C2H5Cl
10. HCl + peroxide give Markonikov’s addition
Cl
HCl
C C C peroxide C C C

INTEXT EXERCISE: 3
1. Oxygen atom which has less electron density is better having group.

2. Oxygen atom which has more electron density is good nucleophile

6.2 Chemistry
3. 6. Fact
7. Fact
8. In protic solvent Nu increases down the group.
4. 9. In aprotic solvent Nu decreases down the group.
10. —O—SO2—CF3—I of 3 F atom and m of two

make ve charge on oxygen stable hence best

leaving group.
5.

INTEXT EXERCISE: 4
1. More stable carbocation give faster rate of reaction:

2. (a) Br is better leaving group then Cl

(b) R—OH better Nu then H2O
(c) Rate [reactant]

5. Rate stability of carbocation

(d) Rate: 30 RX > > 6. Fact

7. Fact

partial double bond of X. 8. 3o RX only give SN1 NO SN2

3. Rate stability of carbocation 9. Fact

Rate strength of leaving group. 10. Rearrangement hence SN1

4.

INTEXT EXERCISE: 5
1. (a) 1o RX rate faster then 2o RX 2. (a) ve charge Nu is better then neutral in case of
(b) C—C==C—C—Br show resonance in transition same atom
state. (b) C2H5S is bettter Nu then C2H5O
N
2 decreases (c) [Et3]P is better Nu then (ph)3N
(d) benzene ring show more resonance in transition (d) rate [reactant]
state.
 Alkyl and Aryl Halides 6.3
5- OH?
Rate 2 = 2 5MeI?
3. Fact
2 = Rate1
4. Fact
5. In SN2 when Nu and reactant both are neutral then rate
8.
of reaction increases as polarity of solvent increases
because transition state become more stable.
1 9. Fact
6. SN2 rate α crowding
10. (a) SNNGP (b) SN1
7. Rate1 = 5MeI?5OH?
(c) SNi
INTEXT EXERCISE: 6
1. Fact
Me
2. Crowding favour elimination and I is better leaving
group then Br 7.

Me
3. doesnot have hydrogen hence

cannot go by E2.
4. (d) cannot go by E2.
8.
5. rate of dehydration stability of product
stability of carbocation
product of (A) and (C) are same but carbocation of
(A) is more stable then (C).

6. 9. rate stability of carbocation

10. Fact

INTEXT EXERCISE: 7
1. Better leaving group give faster rate of reaction.
2. Fact
3. Rate of reaction stability of product. Product of (a) is most stable due to resonance of benzene ring.
4. (a) option form most stable alkene hence fastest reaction.

5.
6.4 Chemistry

6.

7. rate of reaction leaving group strength

8. F is bad leaving group hence carbanion like character.
9. F give Hoffman alkene as major alkene.
10. C—D bond is stronger than C—H bond hence alkene formed by breaking of C—H bond is major.
INTEXT EXERCISE: 8
1. sp3 hybridisation CHCl3 1
6. CHCl3 + 2 O2 HCl + COCl2 (phosgene)
2. CCl3—CH(OH)2 + NaOH CHCl3 + HCOONa +
7. 2CHCl3 + 6Ag
pure H2O
3. CCl3—CH(OH)2 + NaOH CHCl3 + HCOONa + 8.
pure H2O
35H?
4. CHCl3 + Zn + H2O CH4 + ZnCl2 9. Fact
5. Fact. 10. Fact
INTEXT EXERCISE: 9
1. (b) option does not have hydrogen
2. Ph—Cl had doube bond character due to resonance.
1 6.
Bond length α Bond order

remove. Chlorobenzene is ortho para directing.

3.

7.

4. Fact
5. Fact
 Alkyl and Aryl Halides 6.5

8. 9.

10. Fact

EXERCISE 1

1. Fact
17. HS OH TsCl
Py HS OTs
2. AS : CH3 OH < CH3 SH < HCl < HI
BS of CB : CH3 O - > CH3 S - > - Cl > - I HO
!

S
!
OTs
LG: CH3 O < CH3 S < Cl < I
- - - -

Intramolecular
3. For polar protic : Nu -:I - > Cl - SN2
For polar non protic solvent : Nu -:Cl - > I -
S
hence, positive change in rate of Cl - is more.
4. Acidic strength : Ph - SO3 H > Ph - COOH , 18. + m group of carbon increases rate of SN2 reaction
CF3 SO3 H > CCl3 SO3 H, HI > HCN, H 2 O > NH3 19. halo benzene does not give SN reaction due to partial
5. Fact double bond
6. Fact 20. Crowding decreases nucleophilicity
7. Fact 21. Fact.
8. Electron donating group increases nucleophilicity 22. (a) crowding decreases rate of SN2 reaction
9. Fact. (b) Br - is better leaving group than Cl -
10.
(c) crowding decreases rate of SN2 reaction
11. SN2 reaction of OH
(d) m group increases rate more as compare of +
12. Fact. m group.
13. halogen directly connected to benzene ring has 23. R - Cl + NaI R - I + NaCl
Fast
partial double bond and it does not give SN reaction.
R - I + RONa Fast
R - O - R + NaI
14. In (a) there is SNNGP during SN2 because of COO
hence No Inversion. 24. SN2 reaction of - OH
Anhy ZnCl 2
15. SOCl2 + pyridine give SN2 reaction and OTs is 25. 1° ROH 3 , SN 2
R - Cl
leaving group.
26. M group of benzene favour SN2 over SN1
Na2S
16. Cl C C C C Cl Cl C C C C S
DMF 27. Fact
SN2 Intramolecular
SN2 28. SOCl 2 give SNi reaction hence retention of
C C
C C 29. Halogen on bridge head carbon does not give SN
reaction.
S
30. Compound which can form more stable carbocation
undergoes hydrolysis faster.
31. Carbocation form in SN1
carbocation.
6.6 Chemistry
32. Compound with better leaving group react faster.
33. Ethanol is also nucleophile in SN1 mechanism
50.
34.

51. (c) option has no hydrogen hence E1 is no

possible.
35. Reacitivity for solvolysis stability of carbocation
52. Strong base means E1, more resonance during
36. Reactivity for hydrolysis stability of carbocation transition state then more stability.
37. Fact.
38. Fact. 53.
39. Fact.
40. Fact.
41.
OH
H2O C C C
CH3 I CH3 OH + CH3
54. C C C C alc. KOH
" C C C C+C C C C
I! H 2O Cl major,
+ more stable
two types of
CH3 + H3C ! hydrogen

42. Stability of carbocation

55.
43. Stability of carbocation

44.
56. Crowded, hence gives Hoffman alkene as major.
57. Anti elimination is faster and then stability in case of
cycloalkane
45. Those compound can form stable carbocation gives
SN1 reaction
58.
46. more stable carbocation

47.
59. X $ Saytzeff alkene major
Y $ bulky base hence Hoffman alkene major
60. Hoffman alkene is major.

48. Fact.
49. Fact.
 Alkyl and Aryl Halides 6.7
68. Fact

61. 69. Fact

70. Moderate or poor leaving group and strong electron

withdrawing group at carbon favour E1CB

71. D exchange observed in E1CB

72.
62. More stable product have faster rate of reaction
63. Fact

64. Bulky base give Hoffman alkene as major it

is Exocyclic as double bond outside ring.
73.
65. Bulky base Hoffman major.
66.

74. Option d does not have EWG on carbon

67. -
75. X 2 C - CF3, X stabilizes carbanion by I and

EXERCISE 2
1. Nu order: less crowded more nucleophilic

8. Fact: Nu: H > CH3 > OMe > OH > CN

9.

2. Fact
3. m group on benzene ring make ve charge more
stable hence better leaving group 10. aprotic solvent favour SN2 reaction
4. leaving group strength stability of ve charge.
5. Ans option (d) Fact
6. nucleophilicity increases down the group 11.
7. Nu order: ve charge atom of same type more
nuclephilic then neutral OH > H2O
6.8 Chemistry
12. 17. SN2 reaction favour by non protic solvent. Protic
solvent decreases nucleophilicity of Nu.
18. SN2 reaction, rate = K[R—I][131I ]n inversion of

13. Less crowded base will give faster rate

14.

19. SN2
carbon but not at other chiral carbon atoms.

15. SN2 reactions OH replace by Cl

16.

20. Both are SN2 reaction 1° R - X has more stable

transition state then 2° R - X crowding is deciding
factor

24. SN2
21. chiral atom
25. PCl5, S N reaction hence inversion
2

26. SN2 reaction, rate : m of carbon > +m of

carbon > 2oR X > bridge head carbon
27. Fact
28.

22. 1o RX give SN2 reaction, ve charge nucleophile give

SN2 (with 1o and 2o R X)

23. * 29.

*
 Alkyl and Aryl Halides 6.9
30. bridge head halide and vinyl halide does not give SN2
reaction, two OH on same carbon give C==O.
46.
31. SOCl2 + ether give SNi, retention of

SOCl2 + pyridine give SN2, inversion of

32. All reactions are going through SN2 reaction hence

crowding decreases reactivity.
33. 47. SN1 reaction: - Cl leaving group, Inversion and
retention both take place.
34. SN2 reaction CN replace better leaving group Br ,
inversion take place 48.
DMF
35. C 2 H5 Cl + KNO 2 H3 C - CH 2 - O - N = O
36. C 2 H5 Cl ]excessg N ]C 2 H5g4 Cl + 3HCl
NH 3 alc.

37. SN2 reaction Cl replace OH

49. During hydrolysis of ether if acidic medium used
38. then. If it can produce more stable carbocation such
as 3° R + then mechanism SN1 otherwise SN2. Incase
of basic medium reaction is SN2.
39. This solvolysis reaction is SN1 hence 2 step process
50. CH3 - C / CNa is good base and high temperature
Ea1 > Ea2 favour elimination
40. (i) SN2 (ii) SN1 on chiral atom elimination product is major
(iii) SN1 on non chiral atom (iv) SN1 on chiral atom
51.
41. (iii) goes by SN2 hence crowding decide rate
(iv) goes by SN1 hence stability of carbocation
decides rate
42. r1 $ 3° R - Br
r3 $ 3° R - Cl r2 $ 2° R - Cl
-
Br is better leaving group then - Cl and 3° RX
give faster reaction then 2° RX for SN1 type
43. Rate of SN1 decided by stability of carbocation
44.

52.

45. Rate of SN1 stability of carbocation

6.10 Chemistry
60. Highly deactivated halo benzene give nucleophilic
substitution in the presence of strong base
53.

61.

(I) I of 1 NO2 (II) M of 3 NO2

(III) M of NO2 (IV) M of 2 NO2
rate of reaction M effect on benzene ring
rate of reaction: II > IV > III > I
62.

54. Fact
55. Fact
56. As crowding on reactant increases elimination
increases
57. As crowding on base increases elimination increases
63.
58. Fact
64. -
NR3 leaving group gives Hoffman alkene major.
59.
65. Bulky base give Hoffman alkene major.
66. -
F leaving group given Hoffman alkene major
67. Fact

EXERCISE 3

1. Rate of SN1 stability of carbocaton

2.

AcO Ag
3. R - Br SN 2
R - OAc
AcO ggR - BrggAg
-
 Alkyl and Aryl Halides 6.11
4. 11. anti elimination has priority over stability of product
in cyclohexane

12. option (c) has no hydrogen has E2 is not possible

13.
hence attack of nucleophile promoted.
dehydration
14. CF3 - CH 2 - CH 2 - OH CF3 - CH = CH 2
- I group stable produce
other option does not have hydrogen to form
alkene.

15.

neutral nucleophile and room temperature hence SN1

prefered over E1
5. alc AgNO 2
16. C 2 H5 - Br C 2 H5 - NO 2
17. For benzene formation hydrogen should be there
w.r.t to halogen

18.

6. SN1 reaction hence d + l product in almost equal

ratio.

7.

19.

8. rate of E2 leaving ability 20.

I > Br > Cl > F
- - - -

9. P anti elimination more stable

Q hyper conjugation of H is greater then D hence
product of III more stable then IV 21.

R reactivity stability of product

S hydrogen of VII is more acidic hence more
reactive.
10. alc.KOH, anti elimination of HBr
A trans B cis 22. As % of protic solvent increases, stability of
Ph ]CH3gC = C ]CH3gPh
carbocation increases
% of SN1 increases hence inversion decreases
6.12 Chemistry
34. S,R,Q are less stable product hence they are alkene.
E2 reaction as base ve. P has similar energy
level hence its substitution on alkene means SN2
23. (C Cl is more polar than as Nu is ve.
C I bond)
35. Bulky base give hofmann alkene major NR3,
SR2 leaving group give hofmann alkene major.
36. anti elimination of HX not possible in (c) and (d)
nucleophilic substitution. 37. E2 reaction on heating, hofmann alkene as major
product
38. Elimination product are missing
24.

25.

26. Fact
39.
27. Reactivity for S N2:1° RX > 2° RX > 3° RX > PhX

28. $ 3° RX does not give SN2

$ beilstein test given by halide except Floride
$ R - I - I - is good leaving group hence ready
for nucleophilic substitution.
40. Fact
41. Hunsdiecker reaction Please see mechanism in
29. theory
42. CH 2 = CH - CH 2 - Cl decolorises Br2 water
due to double bond
AgNO3 + C 2 H5 OH give
99 white ppt of AgCl due to stable carbocation
% of R = 100 # 100 = 99%
43. (a) No hydrogen hence no reaction
2
% of Recemisation = 100 # 100 = 2%

30. SN2 (b)

care S $ R
44.
31. (a) and (c) has partial double bond character hence
no SN1 and SN2 reaction
32.

33. Fact 45. Only C option has hydrogen on carbon

KOH
CH 2 Cl 2 3
: CHCl + H 2 O + KCl
 Alkyl and Aryl Halides 6.13
46. 54. Ionizing power of solvent dielectric constant of
solvent
55. thionyl chloride + pyridine give SN2 hence inversion

56.

47. Fact
57. 1° RX give SN2 mainly
48.
58. only (a) option have optically active carbon.
59. 1° RX give SN2 reaction
60. (a) $ SN1 hence retention also happen
(b) SN2 only inversion
(c) SNi only retention
(d) SN2 only inversion

61.

49.

50.
62.

Passage (Question. 51 To 53) 63.

64. SN2 reaction

65. It is E1 CB, unimolecular , second order reaction
1 + 2 = 3
66. Nucleophilicity: I - > - CN > EtO - > OH -
6.14 Chemistry

67.

68.

69.

70.

chlorides on vinyl position cannot be replaced

71.

72.

73. (1) alc KOH then (2) NaNH2

 Alkyl and Aryl Halides 6.15

74.

75.

76. All are SN2 reactions 79. (a) SN1 is not given by partial double bond chlorine
Nu Leaving group (b) partial double bond chlorine and 3oRX doesnot
C 2 H5 O - - O - SO 2 - CH3 and (c) give SN2

PH3 -I (d) 3oRX and 2oRX with resonance can give SN1
HC / C - - Br 80. Fact
CH3 - O -
- Cl 81. Fact
77. As crowding increases rate of SN2 reaction decreses 82. Fact
78. 1oRX give SN2 1oRX which can form stable 83. Fact
carbocation give SN1 and SN2 both 3oRX give SN1

Br
KOH (alc.)
3.
1.
!
Ph Ph
Br
C OH
Br Na+OCH3
CrO3/H+ O 4. MeOH

Br
+
O
OH2 O 5.
C Br
does not form alkene with BuONa.
H
+
O H2O
!
6. rate of SN1 stability of carbocation
Br Br
Br
Br
Br2
stability:
2.
OEt
+ Br Br
!
!Br EtOH
7. Bulky base produce Hoffman alkene as major
8. More stable alkene is the major product
Stable carbocation
6.16 Chemistry
9. CH3O favours E2 reaction. 14. Fact
CH3OH favours SN1.
10. NaI is not a base 15. Only (c) option has chiral atom
11. Fact

12.
16.

17. as crowding increses reativity towards SN2 reaction

decreases
13.
18.

19. Fact

1.

P: 5.

6.
Q:

R:

S:

7.

2.

3. Fact

4.
 Alkyl and Aryl Halides 6.17
8. P EAS at ortho position of +m group. 14. IV can go SN1 and SN2 as their is chiral atom so
Q EAS at ortho position of more electron donating
group (+m) I, II can undergo SN2 as well as SN1
I, III can undergo SN1

S EAS at para function 15.

of activiated ring (containing +m group)

9.

16.
10. Fact
11.

12.

13.
6.18 Chemistry