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[[organic c h e m i s t r y !

XII (ALL)

HALOGEN DERIVATIVES

CONTENTS
EXERCISE-I (A)
EXERCISE 1(B)
EXERCISE-II
EXRECISE-III
EXRECISE-IV(A)
EXERCISE IV(B)
ANSWER KEY

EXERCISE-I (A)
(Choose the correct option. Only one is correct)
Qlf Which one is liquid at room temperature:
^
(A)CH3C1
(B)C2H5C1
(C)CH3Br
^L

Q?f

Q.4

Q. 6

(D)C2H5Br

The correct order ofmelting and boiling points ofthe primary (1 ), secondary (2) and tertiary (3) alkyl
halidesis:
(A)P>S>T
(B)T> S>P
(C) S > T > P
(D)T>P>S
Pick up the correct statement about alkyl halides:
(A) They show H-bonding
(B) They are soluble in water
(C) They are soluble in organic solvent
(D) They do not contain any polar bond
What would be the product when neopentyl chloride reacts with sodium ethoxide:
(A) 2-Methyl-2-butanol
(B) Neo pentyl alcohol
(C) Both 1st & 2nd
(D) 2-Methyl-2-butene
Reduction of alkyl halide by LiAlH4 is the type of reaction:
(B) Electrophilic substitution reaction
(A) Nueleophilic substitution reaction
(D) None of these
(C)Electrophilic Addition reaction
2-methyl butanoic acid is formed by the reaction CHC13, NaOH and
(A) Propene
(B)Ethene
(C)l-Butene
(D)2-Butene

Q.7

CC14 + KOH (excess)


end product of the reaction is:
(A) K2C03
(B)C0 2
(C) C (OH)4
(D)HCOOK
Q. 8 The yield of alkyl bromide obtained as a result of heating the dry silver salt of carboxyic acid with
bromine if CC14 is:
(A) 1> 3 >2 bromides
(B) 1> 2 >3 bromides
(D) 3 > 1> 2 bromides
(C) 3 > 2 > 1 bromides
Which of the following statements is invalid:
(A) The more stable the carbocation the faster it is formed
(B) Propyl cation changes to more stable isopropyl carbocation by 1,2 shift of a hydrogen
(C) Isopropyl chloride reacts with sodium ethoxide to form 1-ethoxypropane
(D) Propyl halides reacts with sodium ethoxide to form 1-ethoxypropane
Q.10 Nitrochloroform is prepared by the action of chloroform and:
(A) Hot aqueous solution ofKN03
(B) Hot aqueous solution ofNaN02
(C) Hot concentrated nitric acid
(D) Hot dilute HC1 + aq. NaN02 solution
, Odl Which of the following compounds is most rapidly hydrolysed by S^l mechanism.
(B) C\-CU2-CU=CU2
(A)C6H5CI
(C)(C6H5)3CC1
(D)C6n5CU2C\

o
Q.12 CH3MgBr + CH2 = CH - C - H

2 > product (major), product is

OH
(A) CH2 = C H - C - H

CH3
(C) CH3-CH2-CH2-CHO
faBansal Classes

(B) CH 2 -CH = CH-CH3

OH
(D) None is correct
Halogen Derivatives

[2]

Q.31

n-CjgH^Br + HC =CNa

n BuLi

>A

> B
H /Imc ar scat

5-methyl-1 -hexene + HBr (peroxides) -> C - ^ D

Q.32

Complete the following by providing (A), (B),(C) and (D):

(i)

CHjCH^CHjOH

(ii)

CH3CH2CH2I

PBr

3 > (A)

Alc K0H

A16^011 > (A)

h+/h

> (B)

2 > (B)

HBf

socl

" ' - >E

p6roxybenzoicacid

>F

NH

> (C)

? > (D)

2 > (C)

(D)
LiAlH4

(iii)

CH3CH2CH = CH2 - J i ^ U (A)

Alc K 0 H

> (B)

HBr

> (C)

Light

(iv)

CHgCH^MgBr

CH CHQ/H

2 > (A) - ^ - > ( B )

AlcKOn

> (C)

Q. 3 3 Carry out following conversions.


CI
I
(a) CH3 - CH - CH3

> C^-CHj-CHj-Cl

without using peroxide

(b) CHg-CHj-CHj-Cl

> CH3-CH-CH3

in single step

CI
CH Br

(c)(^J
C1

(d) ^ J j

> j^j

in three steps only

/"\^ C H 2 C 1
> [^J

in three steps only

O
I!
(e) Ph - CH2 - C - CI

Ph - CH^ - CI
O

(QPh-CHj-Cl

(!Bansal Classes

> Ph - CH2 - C - CI

Halogen Derivatives

[19]

EXERCISE-III
Q.l

A primary alkyl halide (X) C4H4Br reacted with alcoholic KOH to give (Y). (Y) reacts with HBr to give
(Z) an isomer of (X). On reacting with alkali metal such as sodium/dry ether gives (S) CgHj8 which was
differentfromthe compound produced when n-butylbromide was treated with Na. What (X), (Y), (Z)
and (S).

Q.2

On electrolysis an aqueous ethanoilc solution of so dium chloride gives sweet smelling liquid (X). (X)
gives isocyanide test and condenses with acetone tofromhypnotic (Y). What are (X) and (Y)?

Q.3

The alkyl halide C4H9Br (A) reacts with alcoholic KOH and gives an alkene (B), which reacts with
bromide to give dibromide (C). (C) is transformed with KOH & sodamide to gas (D) which forms a
precipitate when passed through an ammonical silver nitrate solution. Give the structure formulae of the
compounds (A), (B), (C) and (D) and explain reactions involved.

Q.4

An unsaturated hydrocarbon (A) C6H10 readily gives (B) on treatment with NaNH2 in liquid NH3.
When (B) is allowed to react with 1 -chloropropane, a compound (C) is obtained. On partial hydrogenation
in the presence of Lindlar catalyst, (C) gives (D), C9H18. On ozonolysis (D) gives 2,2-dimethylpropanal
and 1 -butanal. Give structures of (A), (B), (C) and (D) with proper reasoning.

Q. 5

One mole of each bromoderivative (A) and NH3 react to give one mole of an organic compound (B).
(B) reacts with CH3I to give (C). Both (B) and (C) react with HN02 to give compounds (D) and (E),
respectively. (D) on oxidation and subsequent decarboxylation gives 2 -methoxy-2-methylpropane.
Give structures of (A) to (E) with proper reasoning.

Q.6

A chloro derivative (A) on treatment with zinc-copper couple gives a hydrcarbon withfivecarbon
atoms. When 'A' is dissolved in either and treated with sodium, 2,2,5,5-tetramethylhexane is obtained.
What is the original compound A?

Q.7

A primary alkyl halide (A) C4HjBr reacted with alcoholic KOH to give (B). (B) reacts with HBr to give
(C) an isomers of (A). (A) on reacting with sodium gives (D) CgHlg which was differentfromthe
compound produced when n-butylbromide was treated with Na. What are (A), (B), (C) and (D).

Q. 8

One mole of a hydro carbon (A) reacts with 1 mole of bromine giving a dibromo compound C5HJ0Br2.
(A) on treatment with cold dilute alkaline KMn04 solution forms a compound C5H1202. on ozonolysis
(A) gives edquimolar quantities of propanone and ethanal. Deduce structure of (A).

Q.9

A hydrocarbon (A) was found to contain 85.7% carbon and 14.3% H. This compound consumes 1
molar equivalent of hydrogen to give a saturated hydrocarbon. 1 g of (A) just decolourised 3 8.05 of 5 %
solution by weight of Br2 in CC14. Compound (A) on oxidation with conc. KMn04 gave a compound
(C), C4HgO and (B) acetic acid. Compound (C) can easily be prepared by the action of acidic aqueous
mercuric sulphate on 2-butyne. Deduce (A), (B) and (C).

Q. 10 When a hydrocarbon (A) is treated with excess of hydrogen chloride, a dihalogen derivative (B) is
obtained. The compound (B) is treated separately with aqueous and alcoholic KOH to give compounds
(C) and (A) respectively both having three carbon atoms. Compound (C) does not reduce Tollen's
reagent and compound (A) give white precipitate with ammonical silver nitrate. Assign structures to
compounds (A) to (C).

^Bansal Classes

Halogen Derivatives

[20]

Q.ll

An organic compound (A) C7H)5C1 on treatment with alcoholic caustic potash gives a hydrocarbon (B)
C7H14. (B) on treatment with ozone and subsequent hydrolysis gives acetone and butyraldehyde. What
are (A) and (B). Explain reactions.

Q.12 A dihalogen derivative (A) of a hydrocarbon having two carbon atoms react with alcoholic potash and
forms another hydrocarbon which gives a red precipitate with ammonical cuprous chloride. Compound
(A) gives an aldehyde when treated with KOH (aq). What is (A)?
Q.13 A white precipitate was formed slowly when AgN03 was added to a compound (A) with molecular
formula C6H13C1. Compound (A) on treatment with hot alcoholic KOH gave a mixture of two isomeric
alkenes (B) and (C) having formula C6H,2. The mixture of (B) and (C) on ozonolysis furnished four
compounds (i) CH3CHO, (ii) C2H5CH0, (iii) CH3COCH3, (iv) (CH3)2CH. CHO
What are (A), (B) and(C).
Q.14 0.369 g of a bromo derivative of a hydrocarbon (A) when vaporized occupied 67.2 mL at NTP. (A) on
reaction with aqueous NaOH gives (B). (B) when passed over alumina at 250 C gives a neutral compound
(C) while at 3 50C it gives a hydrocarbon (D). (D) when heated with HBr gives an isomer of (A). When
(D) is treated with dil. F^SO^j, (E) is obtained. Identify (A) to (E) and explain the reactions.
Q.15 An organic compound (X) on analysis gives 24.24 % C, 4.04% H. Further sodium extract of 1.0 g of
(X) gives 2.90 g ofAgCl with acidified AgN03 solution. The compound (X) may be represent by two
isomeric structures (Y) and (Z). (Y) on treatment with aqueous KOH solution gives a dihydroxy compound,
while (Z) on similar treatment gives ethanal. Find out (X), (Y) and (Z).
Q.16
0)
(ii)
(Hi)
(iv)

A chloro compound (A) showed the following properties:


Decolourized bromine in CC14
Absorbed hydrogen catalytically.
Gave a precipitate with ammonical cuprous chloride
When vaporised 1.49 g of (A) gave 448 mL ofvapours at STP.
Identify (A) and write down the equations of reactions.

(I%Bansal Classes

Halogen Derivatives

[21]

EXERCISE-IV (A)
Q.l

, Qrf
^

Chlorination oftoluene in the presence of light and heat followed by treatment with aqueous NaOH gives
(A)o-cresol
(B)p-cresol
(C) 2,4-dihydroxytoluene
(D) Benzoic acid
[IIT 1990]
Aryl halides are less reactive towards nucleophilic substitution reaction as compared to alkyl halides due to
(A) The formation ofless stable carbonium ion (B) Resonance stabilization
(C) The inductive effect
(D) sp2 hybridised carbon attached to the halogen
[IIT 1990]
1-Chlorobutane on reaction with alcoholic potash gives:
(A) 1-butene
(B) 1-butanol
(C)2-butene
(D)2-butanol [ITT 1991]
The products of reaction of alcoholic AgN02 with ethyl bromide are
(C) Nitroethane
(A) Ethane
(B) Ethyl nitrite

Q.5

Q.7

<^8

Q.9

[ITT 1991]
(D) Ethyl alcohol

When nitrobenzene is treated with Br2 in presence ofFeBr3 the major product formed is:
m-bromonitrobenzene. Statements which are related obtain the m-isomer are
(A) The electron density on meta carbon is more than on ortho and para position
(B) The intermediate carbonium ion formed after initial attack of Br+ at the meta position is least
destabilized.
(C) Loss of aromaticity when Br+ attacks at the ortho and para position and not at meta position
(D) Easier loss of H+ to regain aromaticityfromthe meta position thanfromotho and para positions.
[ITT 1992]
Arrange the following compounds in order ofincreasing dipole moment
Toluene
m-dichlorobenzene
o-dichlorobenzene
p-dichlorobenzene
I
II
III
IV
(C) IV<I<III<II (D) IV<II<I<III
(A) I < IV < II < III (B) IV<I<II<III
[IIT 1996]
In the reaction of p-chloro toluene with KNHj in liq. NH3, the major product is:
(A) o-toluidine
(B) m-toluidine
(C) p-toluidine
(D)p-chloraniline
[IIT 1997]
(CH3)3CMgCl reaction with D 2 0 produces:
(A) (CH3)3CD
(B)(CH3)3OD
(C)(CD3)3CD
(D) (CH3)3OD [IIT 1997]
Benzyl chloride (CgHjCH^C^canbe preparedfromtoluene by cMorinationwith:
(B) SOClj
(C)C12
(D)NaOCl
(A) S02CI,

[IIT 1998]

0.10

Toluene, when treated with Br2/ Fe, gives p-bromotoluene as the major product, because the CH3
group
[IIT 1999]
(A) is para directing
(B) is meta directing
(C) activates the ring by hyperconjugation
(D) deactivates the ring

0Cfl

The order ofreactivity ofthe following alkyl halides for a S ^ reaction is:
(A) RF > RC > R-Br > R-I
(B) R-F > R-Br > R-Cl > R-I
(C) R-Cl > R-Br > RF > RI
(D) R-I > RBr > R-Cl > R-F

^Bansal

Classes

Halogen Derivatives

[ITT 2000]

[22]

Identify the set of reagents / reaction conditions 'X' and 'Y in the following set of transformation:
CH3 - CH2 - CH2Br

>

Product

> CH3 - CH - CH3


1
Br

(A) X = dilute aqueous NaOH, 20C; Y=HBr / acetic acid, 20C


(B) X = concentrated alcoholic NaOH, 80C; Y=HBr/ acetic acid 20C
(C) X = dilute aqueous NaOH, 20C; Y=Br 2 / CHC13,0C
(D) X = concentrated alcoholic NaOH, 80C; Y=Br2/CHC13,0C
Q.13

CH3MgBr + Ethyl ester - which can be formed as product,


(excess)

[IIT 2003]

CH,

CH2CH3

(A) HO-

[IIT 2002]

" CH2CH2CH3

(B) HO-

-CH 2 CH 3

CH2CH3

CH2CH3

CHjCH^

CH3

(C) HO-

CH 3 '

(D) HOCH,

CH,

Match the following:


Column I
(A) CH3-CHBr-CD3 on treatment with ale. KOH gives
CH2:=CH-CD3 as a major product.
(B) Ph - CHBr - CH3 reacts faster than Ph-CHBr-CD3.
(C) Ph-CHj-CHjBr on treatment with C2H50D/C2H50~
gives Ph-CD=CH2 as the major product.
(D) PhCH^f^Br and PhCD2CH2Br react with same rate.

Column II
(P) El reaction
(Q)E2 reaction
(R) El cb reaction
(S) First order reaction



EXERCISE-IV
Q.l

(a)
jvf
Q.2

Fill in the blanks:


Butan nitrile can be prepared by heating _

(B)

with alcohalic KCN.

[IIT 1992]

Amongst three isomers of nitrophenol, the one that is least soluble in wateris_

[IIT 1992]

Identify the major product in the following reactions:

[IIT 1993]

CI
CgHj CH2 CH - CH3


KOH A


 

(ii)

C6H5COOH + CH 3 MgI-

Q.3

An alkyl halide X of formula CfiH]3Cl on treatment with potassium tertiary butoxide gives two isomeric
alkenes Y and Z (C6H12). Both alkenes on hydrogenation give 2,3-dimethylbutane. Predict the structures
ofX, YandZ.
[IIT 1996]

faBansal Classes

>9+ ?

Halogen Derivatives

[23]

Q. 4

Predict the structure of the intermediates/products in the following reaction sequence - [ET 1996]
Br
HMeOPh

Q.5

_AicohaiicKOH^

BWrite structures of (A) and (B).

Heat

(b)

H1(excess)

(CH3)2CHOCH3

> A+B Write structures ofAandB.

[IIT 1998]

Heat

Q. 6

Complete the following reaction with appropriate structures of products/reagents.

[DT1998]

CH=CH2
Br2

(i)NaNH 2 (3equi.)

(II)CH 3 I

Q.7

What would be major product?

[IIT 2000]

CH,

CH 3 -C-CHBr

CH3

"

c H OH

2 5

>9

Q. 8

How would you synthesis 4 methoxyphenol from bromobenzene in NOT more thanfivesteps? State
clearly the reagents used in each step and show the structures of the intermediate compounds in your
synthetic scheme.
[IIT 2001]

Q.9

An alkene A (C16H16) on ozonolysis give only one product B (C8HgO). Compound B onreaction with
NaOH/I2 yields sodium benzoate. Compound B reacts with KOH/NT^NF^ yielding a hydrocarbon C
(CgHj Q). Write the structure of compound B and C. Based on this information two isomeric structures
can be prepared for alkene A. Write their structures and identify the isomer which on catalytic
hydrogenation (t^/Pd-C) gives a racemic mixture.
[IIT 2001]

Q.10

Give maj or products A, B, C and D in following reaction sequence.

[IIT 2004]

CH2-C1
K C N

DMF

> / a\
( A )

(i)NaOEt/EtOH

r m

(ii)PhCHO/A

>

( B )

H3Oe

.
'

c(i)SOCl2 I
V^v (ii)CH3NH2

^Bansal

Classes

Halogen Derivatives

[24]

ANSWER KEY
EXERCISE-I
Q.l
Q.8
Q.15
Q.22
Q.29
Q. 36
Q.43
Q.50

Q.3
Q.10
Q.17
Q.24
Q.31
Q.38
Q.45

D
B
C
C
B
A
A
B

Q.2
Q9
Q.16
Q.23
Q.30
Q.37
Q.44

A
C
B
D
C
C
B

Q.l
Q5
Q9
Q.13
Q.17
Q.21
Q.25
Q.27
Q.29

D
Q.2
A,C
Q.6
A,C,D
A,B,C, P
B,C,D
Q.10 B,D
A,C,D
Q.14 A,C,D
A,B
Q.18 A,B,C
A,C
Q.22 B,C
A
3, B
2 ,C
1,D > 2
A>2, B>!, C>4, D - 3
( A ) - Q ; ( B ) - S ; ( C ) - R; (D) - P

C
C
A
C
B
C
A

Q.4
Q.ll
Q.18
Q.25
Q.32
Q.39
Q.46

D
C
D
D
B
A
D

EXERCISE-I
Q.3
Q.7
Q.ll
Q.15
Q.19
Q.23
Q.26
Q.28
Q.30

(A)
Q.5
Q.12
Q.19
Q.26
Q.33
Q.40
Q.47

A
C
C
B
C
B
B

Q6
Q.13
Q.20
Q.27
Q.34
Q.41
Q.48

D
A
D
B
C
A
A

Q7
Q.14
Q.21
Q.28
Q.35
Q.42
Q 49

A
D
B
A
A
A
C

(B)
B,C
Q.4
A,B
B
Q.8
A,B,D
A,D
Q.12 A,C,D
B,D
Q.16 A,B,C,D
A,B
Q.20 A,B,C
A,B,C,D
Q.24 B,C,D
A -> 4, B
3,4, C - > 3, D -> 1,2
( A ) - S ; ( B ) - -Q; ( C ) - R ; ( D ) - P
(A)-Q;(B)-- R ; ( C ) - P ; ( D ) - Q

EXERCISE-II

Q.l

(i) CH 3 - CH - CH,,

attack take place on less stericaUy carbon

OH
Q.4

(ii)

Q-5

(A)\TSJ
H

Me
Me
Me
I
I
I
(c) (A) Me - C = CH - Me, (B) Me-C-CH 2 -Me, (C) Me-C-CH 2 Me
OEt

(d)(A) n
1

Me

faBansal Classes

, (B) | 0 | ,(c) | O j
1

OTs

Me

Me

Br

Halogen Derivatives

[25]

OH

OH

Et

Q.6

(b) Ph-C-<^>

^CH2-CH2-OH

(c) Et-CH-Et

o


Q.7

(d)

Q.9

A=

Q.8

O L - C H - C H = CH9

Conversion

Bs

C - C - C = C-C1

CH3

(l)NaNH2

(2) H^/Pd BaS04

Q.10 (a) & (c)


CH3
Q.ll

(a)AsEt-I

(b) B = CH3 - CH - OH

(c) Me2C=CH2
OH

(d) Me2C=CH2

(e) Me-CH-CH2 & Me - OH - CH2


OH

Q.12 The mechanism of

C1CH2CH2CH2CN
(ii)
PhCHF2
(iii)
FCH2CH = CHC02Me
(iv)
Efl
(v)
no reaction
Q.13 (i) Chloroform responds carbylamine test while ethyl alcohol does not. Carbylamine test- The compound
is heated with aniline and alcoholic caustic potash-an obnoxious smell of phenyl isocyanide (C6H5NC)
is produced.
(ii)
Chlorine atoms of chloroform can be easily replaced by - OH group s on treatment with NaOH. Hence
chlorine atoms come in the form of sodium chloride. The solution thus when treated with silver nitrate
solution gives white precipitate of silver chloride. Chlorine atom in vinyl chloride is not readily replaced
by NaOH, hence it does not give precipiatet with AgN03 solution.
(iii)
The two compounds are hydrolysed with aqueous NaOH when 1,1 -dibromoethane form acetaldehyde
while 1,2-dibromoethane gives glycol.
(iv)
Chlorine atom in chlorobenzene is very less reactive, while chlorine in cyclohexyl chloride is very reactive.
Hence the two can be differentiated as above in (ii)
(v)
Apply test (ii) as above; when benzyl chloride gives white precipitate with AgN03 solution, while O
chlorotoluene does not give precipitate. Alternately, the compounds are oxidised when o chlorotoluene
give o-chlorobenzoic acid when benzyl chloride gives benzoic acid (having non chlorine.)
(vi)
n - Hexane does not respond CI" ion test even after fusion with Na and treatment with acidic AgN03.
the remaining three compounds are distinguished by their reactivity with alcoholic AgN03 solution.
^Bansal Classes

Halogen Derivatives

[26]

(a)
(b)
(c)

CH3 -CH=CHC1 (a
CH, = CHCHjCl (an
cHravcivci

Q.14 The elimination ofHI (or DI)


involves breaking up of C - H (or C-D)
elimination is faster in case of CH3 - CH,I.
Q.15

H3C-CH-CH-CH3

KQHW > C H 3 - C = C H - C H 3 + C H 3 - C H - C H = CH2

CH3 CI

CH3

ch3

shydrogenated carbon.

s with I2 to give PI3 a


> + 3I 2 ->2PI 3
t OH + PI3
3RI + H 3 P0 3
Q.21 KCN is an ionic compound [K+(:C =N:)-] in which both C and N carry a 1
to give alkyl cyanide AgCN
N atom and R-N = Cis

faBansalClasse

Q.22 The strong -1. E offluorineatom in F3C - C < produces partial +ve charge on C atom of CF3 which
ultimately increases+ve charge on 2nd carbon atom to destabilize it
F

+5

i
F
In F3C+, the unshared pair of electrons in the p orbitals of each of thefluorineatom are shifted to C+ via
p-p orbital overlapping and thus stablizing F3C+ ion
Q.23 Dry gaseous hydro halogen acids are better electrophile. Also in aqueous solution F^O acting as nucleophile
may produce alcohol.
Q.24 KI reacts with RC1 to form RI. This RI molecule now hydrolysed easily to give ROH because alkyl
iodide are more reactive than alkyl chloride.
RC1 + KI - RI

H0H

> ROH (more fast)

Q.25 The more pronounced the nucleophilic activity ofthe attacking reagent, then the more the SN2mechasnism
will be favoured. Since in SN1 mechanism the raegent doesnot enter into the rate determining step of
ionisation How ever it can also be expected that as the nucleophilic activtiy is so slow that the mechanism
will changefromSN2 to SN1
Q.26 The dielectric constant of water is greater than that of aqueous acetone, and so ionisation of benzyl
chloride is facilitated.
Q.27 On movingfrom3 to 1 alcohol rate of ^ 2 reaction decreases and reaches to minimum and mechanesm
changesfromSN2 to SN1, Then rate of SN1 rate of reaction increases.
Q.28 Anhydrous A1C13 is used as a catalyst infriedelcrafts alkylation.
Q.29 tert-Butyl chloride, sec butyl chloride and CC14 with ale. silver nitrate
Me3C - CI >

">CHC1>CC1 4
c2H^
Br

Q.30

(a)As Q

-10
1=

C ^

CuLi
2

j]

D.

Q f

Hs

o
Q

faBansal Classes

NOMENCLATURE OFORGANIC COMPOUND

[28]

Me

(b) (A) EtO

Me

Pr, (B) Pr
H

Q.31

EtO
H

e
B e C10H21-C^CLi

A = CjqHjj-C^CH

D = C 1Q H 21 - C = C - (CH 2 ) 4 - CH - CH 3

C-C-C-C-C-C-Br
C
E e C1qH21 - C = C - ( C H 2 ) 4 - C H - C H .
H

CH

CH

CH
F-C10H21-C-C-(CH2)4-CH-CH3
H 0
Q.32
(ii)
(iii)
(iv)

C, CH 3 CHBrCH 3 ;
D, CHgCHNE^CHg
(i)A,CH 3 CH 2 CH 2 Br;B, CH 3 CH = CH 2 ;
B, CH 3 CHOHCH 3 ;
C, CH3CHC1CH3;
D, CH 3 CH 2 CH 2
A, CH 3 CH = CH^
A, CH 3 CHBrCH = CIi 2 ; B, CH2=CH-CH=CH2; C, CH 3 CHBrCH=CH 2 & CH 3 CH = C H - C ^ B r
A, CH 3 Clr^CHOHCH 3 ; B, CH 3 CH 2 CHBrCH 3 ; C, CH 3 CH = CH - CH 3

EXER

CISE-III
Br

Q.L

CH3-CH-CH2-CI

CH 3 - C = CH 2

CH.
(X)

CH3-C-CH
CH 3
2 - Bromo - 2 - methyl propane
(Z) (isomer of X)

(CH 3 ) 2 CH CH 2 -CH 2 -CH (CH3).


(2,5 - dimethyl Hexane)
(S)

Q.2

(Y)
Chloretone (Hypnotic)

Q.3

CH 3 CH 2 CH 2 CH 2 Br

CH 3 CH 2 CH = CH,

CH, CH, CH CH,


Br

(A)

Br

(C)

(B)

CH 3 - CH2- C = CH

<P)
<!SBansal

Classes

Halogen

Derivatives

[29]

Q.4

(CH 3 ) 3 C - C 3 CH
(A)

(CH 3 ) 3 C - C =C"Na+

(CH3)3C-C = C H ^ ^ C T ^

(b)

(C)

(CH 3 ) 3 C - C H = CHCH 2 CH2CH 3


(D)
OCH 3

OCH 3

Q.5

CH 3 - C(CH 3 ) - CH 2 - CH 2 NH 2

CH3-C(CH3)-CH2-CH2-Br

(B)

(A)

OCH 3

OCH 3

CH 3 - C(CH 3 ) - CH 2 CH 2 - OH

CH 3 - C(CH 3 ) - CH 2 CH 2 - NHCH 3

(D)

(C)
OCH,
CH3-CH-CH2-CH2-N-N = O
CH,
(E)
Q.6

(CH 3 ) 3 C - C ^ C L

Q.7

CH,

CH,

CH 3

C H 3 - C = CH

H 3 C C CH 3
Br

CH3-CH-CH2Br
(B)

(Q

CH,
(A)
CH,
CH 3 - CH - CH 2 CH 2 - CH - CH 3
(D)

Q.8

CH,

^CH,
C=C
"H

CH,
(A)
CH3 CH 2

Q.9

CH^ CH2

CH 3 -COOH

C = CH - CH,
CH3X

(B)

(A)

<!SBansal Classes

Halogen

Derivatives

;c = o

CH,
(Q

[30]

CI
Q.10 CH3- C = CH
CI
(A)

Q.ll

(B)

CH 3 -(CH 2 ) 3 C-C1
I
CH3

(C)

CH3(CH2)2CH = C(CH3)3

(A)

(B)

Q.12 H 3 C-CHX 2 (X = Halogen)

CH3.
Q.13

(CH3)2CH-CHCH2CH3

(CH3)2CH CH = CH CH3

(A)

(B)

.C2H5

^ C =C
(C)

Q 14 (A) CHGCE^CTYBR, (B) C H ^ H ^ O H , (C) CHGCH^C^OC^C^C^, (D) CHJ-CH-CH^


(E)CH3CH(OH)CH3
Q. 15 (X) C2H4C12, (Y) CI - CHjCHJ - CI, (Z) CH3CH
Q.16 HC^C-CH^Cl
EXERCISE-IV
Q.l
D
Q.2 D
Q.3 A
Q.8 A
Q.9 A,C Q.10 A,C
Q.14 A - Q; B - Q; C - R,S; D - P,S

Q.4
Q.ll

C
D

EXERCISE-IV
Q.l

(A)
Q.5 A,B
Q.12 B

Q.6 B
Q.13 D

Q.7

(B)

(a) propyl chloride, (b) ortho


Br

Q.2

(i) C 6 H 5 -CH = CH-CH3 ; C 6 H 5 -CH-CH 2 -CH 3


(ii) C6H5COOMgI + CH4

^Bansal Classes

Halogen Derivatives

[31]

ch3 ch3

Q.3

ch3

ch3

(X):CH 3 -C CH-CH 3 ;(Y): CH 2 =C CH-CH 3 ;(Z): C H 3 - C CH-CH


ch3 ch3

CI

HQ.4

-Ph

- H (NGP due to MeO, so retention of configuration)

MeOPh

CH 3

Q.5

(a) Cis and trans forms of stibene C6H5CH=CHC6H5;

(b) Cri-j ^>CH1 + CH31


h

Br

Q.6

G=CCH3

C=CNa

,CH-CH 2 Br

CH-J

NaNH,(liq.)

(A)fQ

*(B)

CH,

Q.7

CH 3 -C-CH 2 CH 3
oc2h5
ONa

Br

OMe

NaOH

conc.H,SOd

I C 3 J A high pressure^ [ o )

MejSO^ [ o ]

OMe

OMe

OMe

NaOH
'

SO,H

-Co)-

->(0)

ONa

OH

OMe

OMe

Alternative rout
Br

Br

Br

Br
naoh

o j - ^ ^ i o j

> [ q j ^ l o j - . .

OMe

ONa

SOiH

n a o h

> [ o j - ^ l q .
OH

ONa

Q.9

(A) PhC(Me)=C(Me)Ph

r z "- H 3 > (B) 2PhC - Me

KOH
KU

" > (C) PhCH2Me

NH3-NH3

Two isomers ofA are cis and trans

CN

Q.10 (A)

mBansal Classes

COOH

CONHCH,
!
CH = C

(D)[OJLOj

Halogen Derivatives

[32]

Q.13

Which is incorrect about Hunsdicker reaction?


(A) Only Cl2 can give alkyl halide
(B) I2 will give ester when treated with RCOO Ag
(C) The reaction proceeds through free radical
(D) F2 cannot give alkyl halide

Q.14

Major product for the reaction

->is:
Br

Br

(A)
Br

(C)

(D)
Br
Me

f5

Me

HO|H

Me

H|CI
11

Et

B
Steps I and II are
(A) both SN1

-OH

-> H1

Et

Et

A
(B) both SN2

(C) ISN1, II SN2

(D) I SN2, IIS N 1

Q.16 What are A & B in the following reaction?


CI
Mg/THF

(i)CH3CHO ^
f Jj
(ii)aq.NH4Cl

.
J\.

.^-Br
CHOHCH3

MgCl

(A)
Br

CI

*{S
V

MgCl

CI

&

(B)
MgBr

^-Br

CHOHCHi

MgCl

(C)f|

&
Br

(D) None of these


^-CHOHCH3

Q.17 Ester A (C 4 H 8 0 2 ) + CH3MgBr


(2 pair)

H,0 +

> C4H10O
(alcohol)
(B)
Alcohol B reacts fastest with Lucas reagent. Hence A and B are
O

(A) CH3 - C - O - C 2 H 5 , (CH3 )3 COH

(B) H - C - O - C 3 H 7 , (CH, )2 CHOH

II

II

(C) C H 3 - C - 0 - C 2 H 5 , ( C H 3 ) 2 C H 0 H

faBansal Classes

NOMENCLATURE

(D) H - C - O - C 3 H 7 , ( C H 3 ) 3 C O H

OFORGANIC

COMPOUND

[3]

Q.18 The hydrolysis of alkyl isocyanides (R-CH2-N C) gives


(A) RNHCOOH

(B) R - CH - COOH (C) RNH2 + HCOOH (D) RCH2NH2 + HCOOH


NH2

What is product of the following reaction?


CI

Mg

CI

ET,0

Qc

CI

MgCi

(B)

(A)

\JX*

MgBr

Following reaction is:


H
CH3(CH2)5^

H
i

^CH3

H,C'
(A) SE2
1

B r

(B) SN1

V~V

.(CH2)5CH3

HO-C

X-Br

V^

(D) None of these

(Q

C H 3

(D) SN2

(C) SN

OH-

H A _ A H

Ais:
HOV

(A)

,CH 3

h/LAH

(B)

H\/

\/

oh/V_AH
(D) None

(C) Both

HCOO"
CHCI3 + OHIntermediates ofthis reaction are
(A) :cci:

J&

(B) :CCL

(C) both

Racemic mixture is obtained due to halogenation of:


(A)n-pentane
(B) Isopentane
(C) neopentane

(D) None
(D)BothA&B

> CH3OH + Br
For CH3Br + OH"
the rate of reaction is given by the expression:
Q.24 (A) rate = k [CH3Br]
(B) rate = k[OH"]
(C) rate = k [CH3Br][OH_]
(D) rate = k[CH3Br] [OH"]
Which will give white ppt. with AgN03?
Q.25 (A) \

)CI

(B) ( O V - C I

(C) ( O / ~ c h 2 c i

(D) Both A & C

The reaction of SOCl2 on alkanols to form alkyl chlorides gives good yields because
(A) Alkyl chlorides are immscible with SOCl2
(B) The other products of the reaction are gaseous and escape out
(C) Alcohol and SOCI2 are soluble in water
(D) The reaction does not occurs via intermediate formation of an alkyl chloro sulphite

<!Bansal

Classes

Halogen Derivatives

[194]

Q.27 True about alkyl halides is/are:


(A) Tertiary alkyl halides undergo ^2 substitutions
(B) Alkyl iodides on exposure to sunlight gradually darken
(C) Alkyl chlorides do not give beilstein test
(D) A nucleophilic substitution is most difficult in alkyl iodides
Q.28 The product formed when glycerol reacts with PC15 is(A) 1,2,3-trichloropropane
(B) Glycero monochlorohydrin
(D) All of these
(C) Glycero dichlorohydrin
Q.29 On heating glycerol with excess amount to HI, the product formed is(A)Allyl iodide
(B) Isopropyl iodide (C) Propylene
(D) 1,2,3-tri-iodopropane
To prepare 3-ethyl-3-pentanol the reagents needed are:

(A) CHgCHjMgBr + CH,-C- CH2CH3


Ii
0

(B) CH3MgBr + CH3CH2 - C - CH2CH3


II
O

(C) CH3CH2MgBr + CH3CH2 - C - CH2 - CH3


II
0

(D) CHgCHjCT^MgBr + CH3 - C- CH2CH3


II
O
Non-occurence of the following reaction
Br + CH3OH
> BrCH3 + OH , is due to
(B) Leaving group is a strong base
(A) Attacking nucleophile is stronger one
(C) Alcohols are not good substrate
(D) Hydroxide ions are weak bases
\_J^32 When ethyl bromide is treated with moist AgjO, main product is:
(A) Ethyl ether
(B) Ethanol
(C) Ethoxy ethane
yJJ^f When ethyl bromide is treated with dry Ag^, main product is:
(A) Ethyl ether
(B) Ethanol
(C) Ethoxy ethane

(D) All of the above


(D) All of the above

CH,

Q.34

H-

H_

c H O-

Br
> ? Major product is:
C2H5OH
CH

h3Cx

/H

(A)

H3Cv

/CH 3

(B)

H3Cx

^ch3

(C)

>

H3Cx
(D)

IK

<!Bansal Classes

^D

/
D

Halogen Derivatives

<

^H

C = C
X

\
CH3

[5]

Q35

(A)

Q.36

u O
H - A CH 3

BRH

(A)

Q.39

(B)

LaJ

(B)

(C) both (A) & (B)

(D),

(C)

(D) None is <

E2

JJ

S ) E ^ ^ n e 0 S 8 e n e ^EAylcWoTde

(C) Ethyl alcohol

(A) CH3CHO and PC15


(C) CHj = CH2 and

(B) CH3COCH3 and PC15


(D) CF^ = CHC1 and HCl

CH3 - C - CH3 - i s

il

tij
> (A)

Agp<nvder

> (B)

H s0

* * > Product A, B & C i

(A)]
(C)]
Q.40

(D)]

^r^Trrtiztir

(C)Alkanols ofthe structure CH3CH(OH) - R (where R = H, alkyl or aryl) give i


(D)'

Q.41

042

( A ) Q

CB)|)

( C ) ^

.(D) I

Q. 43 The appropriate naming for the second step in the haloform reaction is:
(A) Halogenation
(B) Dehydrohalogenation
(C) Reduction
(D) Dehydrogenation
Q. 44 Which product is obtained when bleaching powder is distilled with acetone:
(A) CC14
(B) CHClg
(C) CH2C12
(D) CH3C1
Q.45 What will be the reduction product of following reactions:
+2H
Zn/HCl (ale)
CHCI3-

+4H
Zn/HCJ (aq.)
+6H
Zn/H 2 0

(B) CH4, CH3CI, C H ^


(D) CH3CI, CH4, CF^Cl

(A) C H ^ , CH3CI, CH4


(C) CH3CI, C H ^ , CH4
Q.46 Fe/HCl reduction of 'pyrene'(CCl4) gives:
(A) CH4
(B)CH2C12

(C) CHoCl

(D)CHC13

Q. 47 Addition ofbromine on propene in the presence of brine yields a mixture of:


(A) CH3CHClCH2Br and CH^CHBrCI^Cl (B) CH^CHClCF^Br and CH3CHBrCH2Br
(C) CH3CHC1CH2C1 andCT^CHBrCHjBr(D) C^CHCIC^CI and CH3CHBrCH2Cl
0
Q.48

/^Y3
is converted into
I
by:

(A) (i) CH3~ Mgl, H30+ (ii) H2S04, A, (lii) HBr, R202
(B) (i) CH3- Mgl, H30+ (ii) H2S04, A, (iii) HBr
(C) (i) CH3-MgI, H30+ (ii) HBr
(D) (i) HBr, R ^ (ii) CH3-MgI, H30+
Q. 49 To form Malonic acid, by shortest possible route, we have to start a reaction from:
(A) Ethyledine chloride (B) Methyl chloride (C) Methylene chloride (D) Chloro ethan
Q. 5 0 Frankland reagent is:
(A) Dialkyl lithium
(B) Dialkyl Zinc

<!Bansal

Classes

(C)Dialkyl magnesium (D) Dialkyl aluminium

Halogen Derivatives

[197]

EXERCISE-I
(B)
(Choose the correct option. One or more than one are correct)
Q.l

In the given reaction:


H

[X]is:
H

Br

(A)kXJ

(B)rN

(C)

(D)
Br
Br

Q.2

Consider the following statements?


(A)
CHJ-CHJ-CHJ-I will react more readily than (CH3)2 CHI for SN2 reactions.
(B)
CH3-CH2-CH2-C1 will react more readily than CT^-Cf^-CHj-Br for SN2 reaction.
(C)
CH 3 -CH 2 - CH 2 -CH 2 -Br will react more readily than ( C H ^ C - C I ^ - B r for SN2 reactions
(D)
CH 3 -0-C 6 H 5 -Br will react more readily than N0 2 -C 6 H 5 -CH 2 Br for SN2 reaction

Q.3

A solution of (R)-2-iodobutane, [a] = -15.9 in acetone is treated with radioactive iodied, until 1.0% of
iodobutane contain radioactive iodine, the specific rotation of recovered iodobutane is found to be
15.58, which statement is correct about above information.
(A) It has optical purity 96%
(B) % of R in solution is 99%
(C) Racemic mixture is 2%
(D) Final solution is dextrorotatory

Q. 4

Which are possible products in following


CH 3
CH 2 CI

. A
moistAg,U
2
>

CH 2 OH
CH,

CH 2 OH

Xchoh <&< 1

CH

(C)C >

(D)

OH

Q.5

In which product formation takes place according to Hoffinann's rule


e

(A) CH 3 CH 2 - CH - CH 3

t B

" ^0K >

0
CH C

(B) CH 3 CH 2 - CH - CH 3

Br

3 ^OK >

Br
CH 3

(C)

&/
CH 3 CH 2 -CH-N
CH,

faBansal Classes

CH 3

oh

>

CH,

NOMENCLATURE

(D) CH CH C H - C H
S

011

>

S(CH3V

OFORGANIC

COMPOUND

[8]

Q.6

(i)Et2

A+B

> Alcohol

H2Cr 4

> Ketone

CH
(D) Ais isopropyl magnesium iodide

(C)Bis CH3-CHCOCI

H
CH

Q.7

I
H

CH3

CH 3

(A) C H 3 - C H - C H 2 B r

(B) CH3 - CBr - CH.


Br

(C) CH3CH2CH2Br
Q. 8

(D) C H 3 - C H - C H33

Select the correct statementsfromfollowing


(A) CH3 CH2CH2I will react more readily than (CH3)2CHI for
(B) CH3CH2CH2C1 will react more readily than C^CHjCHjBr for
(C) CH3CH2CH2CH2Br will react more readily than (CH^CH-CI^Br for
(D) CH 3 -0-C 6 H 4 -CH 2 Br will react more readily than N0 2 -C 6 H 4 -CH 2 Br for S.

Q. 9

Which of the following will react with AcOAg


(A)R-NH2
(B)R-OTs
(C)R-N 3

^Bansal Classes

Halogen Derivatives

(D)R-Br

[9]

Q.10 Consider the given reaction

H-C-OTS

NaCN

CH3CH2CH-CN

which of following statements are correct for above reaction.


(A) Product formation takes place due to the breaking of O-Ts
(B) The reaction is S n2
(C) The reaction is Sn1
(D) Configuration ofproduct is (R)
Q.ll

Benzoyl chloride is less reactive than acetyl chloride for nucleophilic acyl substitution reaction because
0
(A) - C - group ofbenzoyl chloride is in conjugation with benzene ring. This makes benzoyl chloride
more stable than acylchloride.
(B) CH3- group of acetyl chloride make C-Cl bond stronger due to the +1 effect.
(C) C6H5- group ofbenzoyl chloride make C-Cl bond weaker due to +R effect.
(D) Carbonyl carbon in benzoyl chloride is less electron deficient than acetyl chloride

Q.12 Bromination can take place at

(C)3

(B)5

(A)L

(D)4

Q.13 Which of following will give syn-elimination


(A) CH3CH2CH2-OCOCH3

(B) CH3CH2CH-CH3
CI

II
s

<!Bansal

Classes

CH3

Halogen Derivatives

[10]

Q.14 Which offollowing are correct for given reaction

N-^OH

(A) Major product of reaction is

(B) Major product is


(C) The reaction is thermal elimination reaction
(D) The reaction is cyclic E2 reaction
Q .15 Haloform reaction is given by
(A) All 2 alcohol

(B) All methyl ketones


(D) Chloral

(C) All the compounds having CH , - C - group

Q .16 Identify the compounds that will undergo NGP reaction


(B) CH3-NtICH2CH2CH2Br
(A) CHjCHj-S-CHjCHjBr
(D) CHg-O-CH^CI^CI^Br

(C) C H 3 - C H - C = O

Br

le

O0

Q .17 Which alkyl halide undergo E2 elimination


Br

(A)

CMe3

(B)

CMe,

CMe,

<P)

(C)
Br

Q.18 3-Phenyl-3-pentanol can be prepared from grignard reagent & other component which can be
(A) 3 -pentanone
(B) Ethylbenzoate
(C) Ethyl phenyl ketone (D) Propanoyl chloride
Q.19 In which of following reaction inverted product will obtained.
(A) SN1

(B)Sn2

(QSnNgp

(D)V

Q.20 Rate ofSN2 will be negligible in


Br

(A)
<!Bansal

Br

Br

(B)
Classes

(C)

0>

Halogen Derivatives

Br

"0
[11]

Q.21

Q.22

SN1 & SN2 is not favourable in


(A) HJC = CH-C1
(B) Ph-CHJ-Cl

SN1 & SN2 product are same in (excluding stereoisomer)

(A)

Q.23

Q.24

(D) H ^ C H - C I V C L

(C) Ph-Cl

(B)

CH 3 CI

Rate ofS N 2 depends on


(A) Cone of Nucleophile
(C) Nature of leaving group
CT

NaOI

(D) Ph - C H - CH - CH 3

(Q

(B) Cone of substrate


(D) Nature of solvent

yellnw solid

G can be
(B) C H 3 - C - C H 2 - C " C H 3

(A)CH3-C-OCH3
II
O

(D)

(C) CD3COH

CCH3
o

Q.25

Match the List I (reaction) withList II (reaction intermediate) and select the correct answer using the
codes given below the Lists.
Listn

List I

(A) CF3-CHC12

alc.KOH/A

>

CF2 = CC12

(1)

Transition state

(2)

Carbocation

(3)

Carbanion

(4)

Free radical

CH3
(B) CH3 - C - OH
CH,
(C) CH3-CH2-Br

> CH, - ~C~= CH,


CH,
alcKOH

> CH 2 -CH 2

Br
(D) C H 3 - C - C H 3

CH,

^Bansal Classes

aq.KOH/A

>

CH,

Halogen Derivatives

P2J

Q.26

Match the List I with List II and select the correct answer using the codes given below the Lists.
List I
Listn
(A)E1CB
(1)
Quaternery Amine oxide
(B) Saytzeff alkene as major product
(2)
Xanthate
CI

Q.27

(C)E2

(3)

CH3-CH2-CH-CH3

(D)E C

(4)

C6H5-CH2-CH-CH3

Match List I with List II and select the correct answer from the codes given below:
ListI
List II
(A)

CH 3 -O-SO 2 CH 3 + C 2 H 5 O

(1)

CH3CI^P H 2

(B)

CH 3 -CH2-I + PH 3

(2)

CH 3 -O-C 2 H 5

Q.28

(C)

HC = CNa + CH 3 -CH2-Br

(3)

CH 3 -O-CH 3

(D)

CH 3 -CI + CH 3 -O

(4)

CH=C-CH 2 -CH 3

Match List-I with List-II for given S n 2 reaction & select the correct answer from the codes given below
Z-CHJBR + CH 3 0
List-n
(P)0.1

List-I
(A)H(B) CH 3 (C)C 2 H S -

(R)l

Q.29

\
CH

iftcdl'i

(0)3

CH 3

(D)

Z-CH 2 -OCH 3 + Br

CH

(S)100

Match List-I & List-II and select correct answer


List-I

(P) Ketone

(B)R-MgX + (CH2) 2 0
n-carbon
(C) R - M g X + C 0 2
n-carbon

Adduct

>
(Q) 1 Alcohol (n+ 1) carbon

Adduct

(D) R-MgX + Ph-C=N-

faBansal Classes

H,O

> Adduct

(A) R-MgX + HCHO


n-carbon

List-n

H3

Adduct

>

3 >

(R) Acid (n + 1) carbon

(S) 1 0 Alcohol (n + 2) carbon

Halogen Derivatives

[13]

Q.30

Match the following

List-n

List-I
/OCH
W-

-C>

(A)

CH,CH 2 Q

CH,0
CH,0

>

(P)E1

CH3O

0
II

CB)
CH33
W

CH 3 CH 2 O

CH22CH2Br

(Q)E2

CH,CH,OD

(C)

(R)Elcb

Br
CD)

feBansal Classes

Br
ale. KOH

(S)Ec

Halogen Derivatives

[14]

EXERCISE-II
Q.l
(i)
(ii)
(iii)
(iv)
(a)
(b)

Explain the following giving proper resoning:


Treatment of 1,1 -dimethyl oxirane with sodium methoxide in methanol gives primarily one product. Also
identify the product giving its IUPAC name
Trimethyl amine reacts with alkyl iodide (RI). As the reaction proceeds the reaction rate abnormally
increases, inspite of depleting concentration of reactants.
Optically active 2-iodo butane on treatment with NaI*/Acetone gives a product which do not show
optical activity.
In the solvent DMSO the order of reactivity of halide ions with methyl bromide is F~ > Cl > Br" > I~
opposite to that observed in methanol solution.
(n - C3H7)3N + CH3I -(n - C3H7)3NCH3+
Relative rate: in hexane, 1; in chloroform, 13000
Br- + CH3OTs-CH3Br + TsORelative rates: in methanol, 1; in HMPT, 105.

(v)

Although ethers are weakly polar, are used as solvent of choice for Grignard reagents.

(vii)

Treatment of either CH3-CH - CH-CHjBr or CH3-CH -CH - CH2 with aqueous HO~ gives the
O

same product. Also write down mechanism involved, & IUPAC name of product.
Q.2
(a)
(b)
(c)
(d)
(e)

On reaction between an alkyl halide and KOH in a mixture of water and ethanol, compare the two
mechanisms SNj and SN2:
relative rates of CH3X,C2H5X,iso-C3H7X&tert-C4H9X
relative rates for RC1, RBr and RI
effect on rate of a rise in temperature
effect on rate of increasing water content of the solvent.
effect on rate increasing alcohol content of the solvent.

Q.3

In the following reaction is carried out in the weakly ionizing solvent, acetone (CH3)2C=0. (Bsisbrosyl,
p-bromo benzene sulfonyl)
n-C4H9OBs + X >n-C4H9X + BsOThe order of reactivity of halide ions depends or the salt used on their source :
ifLi+X~ isused,I^r-^Clif (n-C4H))4N+ X - is used C l - > B r - > I ~
How do you account for this contrast in behavior ?

Q.4

Which of the following is the correct method for synthesizing 4,4-dimethyl-pent-2-yne, using sodamide
in liquid NH3? Given reasons.
CH3
(i) CH3C=CH + CH3 - C - Br

CH3
>

(ii) CH3 - C - C = CH + CH3I >


CH3

CH3
Q.5
(a)

Give the products andfindall unknowns.


I^N CH2 CH; CH, C ^ Br A >

faBansal Classes

Halogen Derivatives

[15]

C2H5O

CH3

(b)

C 2 H 5 OH

CH3-C-CH2-Br
CH3
H

Nal

H
TsCl v *
A
Pyridine

(C)

NaBr

CH, OH

Find out the unknown alphabets.

Q.6

'CH3 + CH3CH2MgBr(l eq)

(a)

H3 +

> A

MgCl

(b)

Ph-OCl +

o
(2 eq)

(c)

H - C -OEt + CHgCHjMgBr

h3o+

(2 eq)

(d) QCMgI +

(1 eq.)
CH2
HCl



H3C

> E

Ph
C2H5

Q.7

To prepare <J>-C-C2H5 by RMgX which is the incorrect pair

(a)

OH
<J)MgBr + (C2H5)2CO

(b)

C2H5MgBr +

^>C =0
H

(c)

H,0

C2HsMgBr + <j>-COOCH3
<!SBansal

>

5C2

Classes

z >
Halogen Derivatives

[16]

(d)

H2

<f>MgBr + C2H5COOCH3

>

I
H
Ci

Q9

Zn
.
Zndust' A n

I
CH3-CH-CH-C
CH
H 2, -- C
C 1I

--

convert?

CH3
Q.10
(a)
(b)
(c)
(d)

What is/are the limitation in the formation of Grignard reagent by RX+Mg dryether >
R should not contain any acidic group
R should not contain any electronegative group
Alkyl halide should not be vicinal dihalide
Alkyl halide can't be Tertiary.

Q.ll

Identify the unknowns

(a)

CH^jCHjCl + 1 ~ - A

(b)
(c)
(d)

(CH3)2CH-Br + KOH (aq.) B


(CH3)3C-Br + KCN (ale.) -> C
(CH3)3C-Br + KOH (aq.) -> D
CI

CH 3 -CH-CH 2 -OH

Conc NaUH

) E,

Q.12 Write major product of the the following reactions:


0)

C l C ^ O ^ C H ^ r + KCN

(ii)

PhCHO

Oii)

BrCH2CH = CHC0 2 Me

(iv)
(v)

EtOH + HI
>D
EtOH + HCN
>E

>A

SF

* >B
^

>C

Q.13

State at least one characteristic test which can distinguish:

C 2 H J O H f r o m CHC1 3

(ii)
(iii)
(iv)
(v)
(vi)

Halogen atoms present in CHC13 and CH2 = CHC1


1,1- dibromoethane from 1,2-Dibromethane
Chlorobenzenefromchlorocyclohexane
o-Chlorotoluenefrombenzyl chloride
n-Hexane, CH3CH = CHC1, CH2= CHCH2C1 and O ^ O ^ C I ^ C l

Q 14 CH3-CH2I reacts more rapidly with strong base in comparison to CD-^CI^I

<!SBansal

Classes

Halogen Derivatives

[17]

Q. 15 2-chloro-3-methylbutane on treatment with alcohoilc potash gives 2-methylbutene-2 as major product.


Q.16 Iodoform gives precipitate with AgN03 on heating while CHC13 does not.
Q.17 Hydrogen atom of chloroform is definately acidic, but that ofmethane is not.
Q.18 A small amount ofalcohol is added to chloroform bottles.
Q. 19 Treatment of Me3CCH = CH2 and Me3CCHOHMe with concentrated hydrochloric acid gives the
same two isomeric alkyl chlorides what are these two products.
Q.20 Iodine reacts with alcohols to give alkyl iodine only in presence of phosphorous.
Q.21 KCN reacts with R - 1 to give alkyl cyanide, while AgCN results in isocyanide as major product.
Q.22 The carbocation F 3 C - C < is unstable whereas carbocation F3C+ismore stable.
Q. 23 Dry gaseous hydro halogen acid and not their aqueous solutions are used to prepare alkyl halides from
alkenes.
Q. 24 RC1 is hydroly sed to ROH slowly but reaction fastens on addition of KI.
Q.25 The mechanism of decomposition of Me3 S+ OH" is SN2 whereas of Me3S+1- is SN1.
Q. 26 Alkaline hydrolysis ofbenzyl chloride in 50% aqueous acetone proceeds by both ^ 2 and S^l mechanism,
when water is used as solvent, mechanism was now mainly SN1.
Q. 27 Ethanol is less reactive than methanol as well as isopropyl alcohols when treated with dry HCl gas.
Q.28 Anhydrous A1C13 is used as a catalyst infriedelcrafts alkylation.
Q.29 Arrange following compounds according to their reactivity with ale silver nitrate.
t-Butyl chloride, sec butyl chloride and CCL.
Q.30


 CH? - OH

- ^ A - ^ B
J.IMID4

^ q)Li a ^
(ii) CuF

+B

NBS

C
1 C

ale.KOH.

CH,
(b)

OH

CH3CH2CH2
H
(i)TsCl
kii)C2HsO"K+
(A)

Hi) K
kii)C2H5OTs
(B)

What are (A) and (B) explain giving their stereochemistry.


^Bansal Classes
Halogen Derivatives

[18]

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