Organic Compounds Containing Halogens

DPP – II
Level – I : JEE(Main) + NEET

1. (d)
a) CH3 – CH = CH2 + HCl 
Peroxide
 CH3  C H  CH3 No Peroxide effect with HCl
|
Cl
b) CH3 – CH = CH2 + HCl 
 CH3  C H  CH3
|
Cl
c) CH3  CH  CH2  Cl2 
 CH3  C H  CH2 
Aq.KOH
 CH3  CH  CH2
| | | |
Cl Cl OH OH
d) CH3  CH2  CH2  OH 
SOCl2
Py
CH3CH2CH2Cl 1  Chloropropane 
2. (a)
For chloroalkanes using conc. HCl and Anhyd. ZnCl2
3. (c)
No Reaction in (c) as OH group can’t be replaced by ClƟ .

a) CH3CH2OH + HCl 

ZnCl2
 CH3CH2Cl
b) CH3  CH  CH2 
SO2 Cl2
475 K
 CH2  CH  CH2 (Allylic substitution)
|
Cl
c) No Reaction
d) CH3COOAg  Br2 
CCl4
Re flux
 CH3Br (Borodine Hundsdiecker Reaction)
4. (c)
Birnbaum Simonini Reaction.
O O
|| ||
R  C  O Ag  Br2 
 R  C  OBr  AgBr
O O
|| ||
R  C  OBr 
 R  C  O  Br
O
||

R  C  O   R  CO2

For Bromides : R  Br 
 R  Br (Major product)
O O
|| ||
For iodides : R  C  O  R 
 R  C  OR (Major Product)

O O
|| ||
 CH3CH2  C  OAg 
 CH3CH2  C  OCH2CH3
Alkyl propanoate
R Ethyl propanoate
Silver propanoate

5. (c) Swarts Reaction

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6. (b)
Alkyl fluorides can be prepared by action of mercurous fluoride or antimony trifluorides (inorganic fluorides)
on corresponding alkyl halide. This reaction is known as Swarts reaction.
CH3Br  AgF 
 CH3F  AgBr
Methyl fluoride

But, when action of Nal/acetone takes place on alkyl chloride or bromide, alkyl iodide forms. This reaction is
called ‘Finkelstein reaction’.

C2H5Cl 
NaI
acetone
 C2H5I  NaCl

Free radical fluorination is highly explosive reaction. So not preferred for the preparation of fluoride.
7. (d)
3o alcohols are most reactive and 1o alcohols are least reactive. Reactivity of 1o alcohol is enhanced by
addition of Lewis acid like ZnCl2.
8. (c)
Br
+
CH CH CH3 CH CH2CH3 CH CH2 CH3
HBr

More stable

9. (c)
Br
|
CH2  CH  CH  CH2  HBr  CH2  CH  C H  CH3 C H2  CH  CH  CH3
At  80o C the product is |
1, 2  addition Br o
At 40 C the product is
1, 4  addition

10. (a)

Water adds directly to the more reactive alkene in presence of a strongly acidic catalyst forming alcohols.

Addition occurs according to Markonikov’s rule.

H SO
CH3  CH  CH2  H2O 
2 4
 CH  C H  CH3
|
OH
o
2 alcohol

CH3 CH3
H2SO4
CH2 + H2O CH3 C CH3
CH3 C
OH
3o alcohol
Note : Addition follows Markownikoff’s rule. Intermediate formed is a carbocation.
11. (b)

2
The reaction following Markownikoff rule which states that when unsymmetrical reagent adds across
unsymmetrical double or triple bond the negative part adds to carbon atom having lesser number of
hydrogen atoms.
Br
|
HBr
CH3  C  CH  HBr  CH3  C  CH2  CH3  C  CH3 .
| |
Br Br
2, 2  dibromo propane
12. (d)

HOCl polarises to give HOΘ and Cl

CH2 CH CH3
More stable intermeidate
CH2 CH CH3 + Cl Cl

CH2 CH CH3

Cl

OH CH CH3
CH2 CH CH3 CH2

Cl OH
Cl
13. (d)
Attachment of electron donating group (+ R or + I) with sp 2-carbon of an unsymmetrical alkene supports
Markownikov’s addition rule through electrophilic-addition-pathway.
But, attachment of electron-withdrawing group (– R or – I) for the same will follow anti-Markownikov’s
pathway (even in absence of organic peroxide which favours free radical addition) through electrophilic
addition pathway.

The product formed by given alkenes when treated with HCl.

+R +  Cl
H Cl Cl Cl
Cl CH CH2 CH CH3 Cl CH CH3
Slow fast
Similarly,
Cl
+ 
H Cl + Cl
H2 N CH CH2 NH2 CH CH3 NH2 CH CH3
Fast
(+R)
+ 
H Cl + Cl
CH CH2 CH3O CH CH3 Fast CH3O CH CH3
CH3O
(+R) Cl
 +
Cl H
HCl Cl
F3C CH CH2 Slow F3C CH2 CH2 F3C CH2CH2Cl
Slow
(I)
Cl
14. (d)
The major product obtained in the given reaction is CH3C(I) (Cl) CHD2.
 
CH3C ☰ CH   CH3C(l)(Cl)CHD2
1. DCI 1 equiv.
2.Dl

Addition in unsymmetrical alkynes takes place according to Markovnikov’s rule.

3
Reaction proceed as follows :
Cl Cl
DCl | |
CH3 C  CH 
(1 equiv.)
 CH3 C  CHD 
Dl
 CH3  C  CHD 2
Prop 1 yne |
I
Product

15. (d)
Addition of HBr to unsymmetrical alkene take place to Markownikoff’s rule.

CH3 CH3 CH3 CH3

CH3
Br Br Br
H + Br Br H+ Br

Br
NO2 NO2 NO2 NO2 NO2
(Major prodcut)

Hence, the correct option is (d).

16. (a)
Carbocation B is more stable due to more hyperconjugation and formed relatively at faster rate compound
to A.
+ Br
+ HBr +
2o carbocation
(B)
But-1-ene
+ Br
+
1o carbocation
(A)

Carbocation B is more stable as it is secondary carbocation having more number of -hydrogen, having a
greater + l effect and formed with faster rate due to low activation energy.
17. (c)

1-chloro-1-methylcyclohexane.

CH3
Cl

CH2 CH3 CH3

Cl
+H Cl + Cl

CH3 CH3 CH3

H Cl
H
+H Cl + Cl

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18. (a)
CH3 CH3 CH3
H+ H2O
CH3 C CH CH2 CH3 C CH CH3 CH3 C CH CH3

CH3 CH3 H3C OH

(Minor)
1, 2-methyl shift
OH CH3
R
CH3 C CH CH3 CH3 C CH CH3

CH3 CH3 CH3

3 cabocation o (Major)
(more stable) (B)
19. (b) We know that in case of an unsymmetrical alkene there is the possibility of forming two products. In
such case the formation of major product is decided on the basis of Markownikoffs rule which is
rationalized in terms of stability of the carbocation. Also 3 carbocation is more stable than 2 carbocation
and 2 carbocation is more stable than 1 carbocation.
H3C
CH CH CH2
H3C 3-methyl-1-butene

CH3 CH2 (1o)

CH CH2
CH3
+H+
CH3 + (2o)
CH CH3 CH3
CH3

Of the two possibilities 2 carbocation is more stable so the product of the reaction is expected to be
predominantly formed by 2 carbocation i.e.
CH3 CH CH CH3
CH3 Br
i.e. 2-Bromo-3-Methylbutane
However some electrophilic addition reaction form products that are clearly not the result of the addition of
electrophile to the sp2 carbon bonded with the most hydrogen and the addition of a nucleophile to the other
sp2 carbon. In the above case the major product formed is 2-Bromo-2-methylbutane.
The unexpected product results from a rearrangement of carbocation intermediate. Please note that all
carbocation do not rearrange.
CH3 CH3 CH3

CH3 C CH CH CH2 + HBr CH3 CH CH CH3 + CH3 C CH2 CH3

Br Br
2-Bromo-3-methylbutane 2-Bromo-2-methylbutane
20. (d) In presence of peroxide, HBr adds on alkenes according to anti-markownikoff’s rule.
Peroxide
H3CCH  CH2  HBr 
 H3CCH2CH2Br
Propene npropyl bromide
Kharasch observed that the addition of HBr to unsymmetrical alkene in the presence of organic peroxides
follows an opposite course to that suggested by Markownikoff. This is termed anti-Markownikoff or
peroxide effect.

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21. (a) Peroxide effect is observed only in case of HBr. Therefore, addition of HCl to propene even in the
presence of benzyoyl peroxide occurs according to Markovnikov’s rule :
HCl
CH3  CH  CH2  CH3  CHCl  CH3 .
 C6H5CO2 O2
22. (c) The given reaction proceeds in two steps :
Step 1. : Addition of H+ or attack of alkene on H+
H

Ph Br + Ph Br
Br Ph
H

Major H
(Resonance effect) Minor
(+R) of phenyl) (I-effect of Ph Br)
Step 2. : Addition of Br– to carbocation.
Br
Br Ph
Br
Ph
Br
(P)
(Major product)
23. (1143)
Br
+ Br2
(C5H10) (C5H10Br2)
Br
Moles of Br2 = moles of C5H5
w 5 5  160
  w g
160 70 70
= 11.428 g = 1142.8  10–2g.

Level – II : JEE(Advanced) / AIIMS / KVPY / Olympiad

24. (a)

CH3 CH3 CH3 CH3

+ Cl
CH3 C CH CH2 + H+ CH3 C CH CH3 CH3 C CH CH3 CH3 C CH CH3
+
CH3 CH3 Cl CH3
CH3
25. (a)

+ +
O2N CH CH CH3 + H+ O 2N CH CH2 CH3 + O2N CH2 CH2 CH3

less stable More stable

Cl Cl

O2N CH CH2 CH3 O2N CH2 CH CH3

Minor Major

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26. (b)

CH3 O + H+ CH3 O
+ +
CH CH CH3 CH CH2 CH3 + CH3 O CH2 CH CH3
More stable less stable
Br
Br
Br
CH3 O CH CH2 CH3
CH3 O CH2 CH CH3
Br
Major minor

27. (b)
BrCN 
 Br+ + CN–

CN Br

H
+
+ Br + CN
Br

Br

CN
H
CN
CN– attacked at less hindered site of cyclic intermediate.
28. (a)

+
H+ + +
+

(I) (II) (III) (IV)

(I) gives (c)
(II) gives (b)
(IV) gives (d)
Carbocation corresponding to (a) is not formed as intermediate.
29. (c)
Me
Me Me
Me Br
Me
RS
R HBr R + Me
Products are (let) R Br (let)
(let)

30. (a)
+
CH3 Br
+ Br
31. (d)

7
Br
+
+ H+ Br

More stable No chiral carbon

32. (a)

At low T, 1, 2-addition takes place at more substituted alkene.

33. (c)
In this reaction there are two intermediate carbocations and the final product is more stable (has less
energy) as it has no angle strain. Also 2nd intermediate is more stable than first.

I = Intermediate
E
I1

I2

34. (a)

+ H+ + +
CH CH CH CH2 + CH2 CH

More stable less stable

Br Br
Br

CH CH2 CH2 CH

Major Br
Minor
35. (a)
Gives PBr3  SN2 Reaction
(b) No reaction in alcohols (c) Rearrangement (d) No reaction.
36. (a)
Anti addition of Br2 on trans alkene provides meso compound.
CH3
H3C H
CCl4 H Br
C C + Br2
H Br
H CH3 CH 3
Trans Meso
Trans-Anti-Meso
37. (c)
Anti-Markovnikoff’s addition of HBr is observed only with unsymmetrical alkenes, a, b, and d
CH3CH  CH2 CH2  CHCH2CH3 CH3CH  CHCH3 CH3CH  CHCH2CH3
 a b  c  d
38. (c)
Peroxide effect is effective only in case of HBr and not in case of HCl and HI

Step : I (a) R – O – O – R  2RO
Step : I (b) RO + H – X  RO – H + X

8
 
Step : II RCH = CH2 + X  R C CH2 X  R 'CH  CH2
 more stable  |
X
 less stable 

R – CH – CH2X + HX  R – CH2 – CH2X + X
For HCl, Step – I (b) is endothermic while step – II is exothermic but for HI, Step – I (b) is exothermic while
Step – II is endothermic.
39. (a)
2 4 HBr (1 eq.) Br

1 3 (1, 2-addition Markovnikov's rule)

2-methylbuta-1, 3-diene
40. (d)
Peroxide effect is not effective in the case of HCl and HI. It is effective only in the case of HBr.
CH3 CH Peroxide
CH2 + HI
Propene (Markovnikov's rule)

CH3 CH CH3

I
2-Iodopropane
2o free radical is more stable than 1o free radical
41. (a)
OH
H+/H2O

Mechanism electrophilic addition reaction of alkenes

42. (c)
Anti-Markownikov Addition.
43. (b)

CH2  CH  CH2OH   CH2  CH  CH2Br  H2O

Conc.
HBr