SECTION IV Subjective Questions

LEVEL I
1. An organic compound (A) C
6
H
10
on reduction, first give (B)
6 12
C H and finally (c)
6 14
C H
. (A) on reaction with ozone followed by hydrolysis in presence of Zn gives two
aldehydes
2 2 2
C H O (E). Oxidation of (B) with acidified
4
KMnO gives acid (F)
3 6 2
C H O .
Determine structures of (A) to (F) with proper reasoning.
2. Identify (a) the chiral compound C,
10 14
C H , that is oxidized with alk.
4
KMnO to
PhCOOH, and (b) the achiral compound D,
10 14
C H , inert to oxidation under the same
condition.
3. An alkyl halide, (X), of formula
6 13
C H Cl on treatment with potassium tertiary butoxide
gives two isomeric alkenes Y and Z
6 12
(C H ) . Both alkenes on hydrogenation gives 2, 3-
dimethylbutane. Predict the structures of X, Y and Z.
4. a)
2
Br (A) +
CH
3
H Ph
H
HBr/peroxide
(B)

Identify A and B
b) Write the product(s) of the following reactions:

Peroxide
3 2 3
CH CH CH BrCCl ? = +
5. Write the major products of the hydroboration and oxidation of:
a) 1-Ethyl cyclopentene
b) Methylene cyclopentene.
6. Give the missing compounds in the following:
a)
3 3
BH .THF CH COOH
? ?

b) 3 3
BH .THF CH COOH
? ?

c)
3 3
BH .THF CH COOH
? ?

d)
3
3
(i) BH .THF
(ii) CH COOH
?

7. Complete the following equation:
a)
2 2
H H
3 3 3 2 2 3 Pt Pt
CH C CCH (A) CH CH CH CH
b)
2 5
Na C H OH
3 3 2 5
CH C CCH (B) NaOC H
+
+
8. a) Starting with any alkyne, prepare ethyl cyclohexyl ethyne.
b) Starting with cyclohexyl ethyne, prepare acetyl cyclohexane.
9. a) Complete the following reactions:

2 3 2 2 2 2
Al O , NaNH C H H (1 equiv) H
3 3 Pd 400 C
CH COCH A B C D E
+
A

b) Complete the following reactions:

2 2 2 2
3 2
i ) NaNH H CH I
3 ii ) CH CH Br Lindlar's catalyst Zn(Cu)
CH C CH A B C
10
CH
3
3
HCO H
X
4
KMnO ,
Y
A

3 2
O , H O
Z (mix)

Identify X, Y and Z
LEVEL II
1. Predict the product of the following
a)
OH
2 4
conc. H SO /
HCl
A
B
A

b) 2
2 6
2 2
2
4
H O/ H
(i) B H
(ii) H O (OH )
(i) Hg(OAc)
(ii) NaBH
A
B
C
+

C H
3
CH
2
CH
3
CH
3

c)
OH
3 2
RCO H H O H
J
+


2. a) Give reasons for the following:
When 1-penten -4-yne is treated with HBr in equimolecular proportion, the addition
takes place on double bond and not on triple bond yielding thereby the product
CH
3
CH(Br)CH
2
CCH.
b) Provide a suitable mechanism for the following reaction.
CH
3
OH
CH
3

3. Three isomeric alkenes A, B and C, (
5 10
C H ) are hydrogenated to yield 2-methylbutane A
and B gave the same 3 ROH on oxymercuration demercuration B and C give different
1 ROHs on hydroboration oxidation supply the structures of A, B and C.
4. 3, 3-dimethyl-1-butene and Hl react to give two products,
6 13
C H l . On reaction with alc.
KOH one isomer, (I) gives back 3, 3-dimethyl-1-butene the other (J) gives an alkene that
is reductively ozonized to
2
Me C O = . Give the structures of (l) and (J) and explain the
formation of the latter.
5. a) Identify X, Y and Z in the following sequence of reactions giving stereo chemical
structures wherever possible.

3 3 2
4 2
(i) CH CO H (i) H (i) Na
(ii) Br Pd BaSO (ii) H / H O
C CH (X) (Y) (Z)
+

b) Complete the following sequences
i)
3
AlCl
3 2 2
CH CH CH Cl +

ii)
2 2
3
Br i) NaNH (3 equi.)
6 5 2 ii) CH I
C H CH CH A B

=
6. Hydrocarbon (A) C
6
H
10
on treatment with H
2
/Ni, H
2
/Pd BaSO
4
and Na/liquid NH
3

forms three different reaction products (B), (C) and (D) respectively. (A) does not form
any salt with ammoniacal AgNO
3
solution but forms a salt (E) on heating with NaNH
2
in
an inert solvent. Compound E reacts with CH
3
I to give (F). Compound (D) on oxidative
oznolysis gives n-butanoic acid along with another product. Give structures of (A) to (F)
with proper reasoning.
7. A hydrocarbon (A) containing 90% carbon reacts with dil. H
2
SO
4
in presence of HgSO
4

to give (B). Compound (B) is reduced by LiAlH
4
to (C) which on heating with H
2
SO
4

gives (D) directly by hydrogenation in presence of deactivated Pd-CaCO
3
catalyst.
Outline the reactions.
8. Identify the missing compound in the following sequence of reaction:
i)
2 2 2 2
H O H Br NaNH KOH(alc.)
2 Lindlar's catalyst H
CaC (A) (B) (C) (D) (E)
+
A

ii)
2
2 4 2 4 2
2
2
4H O LiAlH Conc. H SO Br H / Hg
2 3 H O
NaNH
Mg C (A) (B) (C) (D)
(E) (F)
+ +
A
A

iii)
2 2 4 4
Br / h Br / CCl KMnO alcoholic KOH alcoholic KOH
3 2 2 3 1 mol
H
CH CH CH CH A B C D E
+
v

9. An hydrocarbon (A), C
8
H
14
, decolourises Br
2
/CCl
4
and cold dil. neutral KMnO
4
solution,
but does not react with ammonical AgNO
3
and Cu
2
Cl
2
solutions. It on ozonolysis
produced two molecules of the same acid (B), C
4
H
8
O
2
, which on heating with sodalime
gave propane. What are (A) and (B) ?
10. A hydrocarbon (A) is treated with excess of HCl to give a dihalogen
compound (B), Subjective
Problem 1: 2-Butyne undergoes following reactions in steps as indicated. Identify A to H.

2 2
2
H D / Pt
3 3 Ni B(P2)
CH C CCH A B
2
D / Pt Na / EtOH
C D
2 2
2
H Br
Ni B(P2)
E F
2 2
Br H
Ni
G H

Solution:
A is obtained by syn addition A =
C H
3
H H
CH
3
cis

B is also obtained by syn addition B =
meso
C H
3
H
D D
H
CH
3

C is obtained by anti addition C =
H
C H
3
H
CH
3

D is mix of d- and l- (reacemic mixture) D =
d- and l-(racemic)
C H
3
H
D H
D
CH
3

E is obtained by syn addition E = as A
Addition of
2
Br is anti
F =
racemic
C H
3
H
Br H
Br
CH
3

G =
C H
3
Br CH
3
Br

H = as F
Problem 2:
3(l)
Li, NH
n BuC CMe A
4 2
dil.KMnO / H O
3 2
HCO H/ H O
2
H
Lindlar's catalyst
B
C

Identify A, B and C with proper explanation.
Solution:
n - BuC C H
H CH
3
n - BuC C H
C H
3
H
A-trans
B-cis
3
HCO H
Li,
3
NH
2
H
Lindlar's catalyst
(by anti addition)
(by syn addition)
O H
CH
3
H
H OH
n-Bu
(C) - and its enantiomer (racemic)
n BuC CMe
4
KMnO

Problem 3: One mole of a hydrocarbon (A) reacts with one mole of bromine giving a dibromo
compound
5 10 2
C H Br . Substance (A) on treatment with cold, dilute alkaline
4
KMnO solution forms a compound
5 12 2
C H O . On ozonolysis (A) gives
equimolar quantities of propanone and ethanal. Deduce the structural formula
of (A).
Solution:
3
2
i) O
ii) H
A Propanone + ethanal
So, A is

CH
3
C H
3
C H
3
2-methylbut-2-ene


CH
3
C H
3
C H
3
2-methylbut-2-ene
2
Br +
C H
3
CH
3
Br
Br
CH
3
2,3-dibromo-2-methylbutane


CH
3
C H
3
C H
3
2-methylbut-2-ene
4
alk. KMnO + C H
3
CH
3
OH
CH
3
OH
2-methylbutane-2,3-diol

Problem 4: An unsaturated hydrocarbon A
6 10
(C H ) readily gives B on treatment with
2
NaNH in liquid
3
NH . When B is allowed to react with 1-chloropropane a
compound C is obtained. On partial hydrogenation in the presence of Lindlar
catalyst, compound C gives D
9 10
(C H ) . On ozonolysis D gives 2, 2-dimethyl
propanal and 1-butanal. With proper reasoning give the structures of
A, B, C and D.
Solution:
A =
C H
3
CH
3
CH
3
H

B =
C H
3
CH
3
CH
3
C
Na


C =
C H
3
CH
3
CH
3
CH
3

D =
C H
3
CH
3
CH
3
CH
3

Problem 5: A compound (X) when passed through dil
2 4
H SO containing
4
HgSO gives a
compound (Y) which on reaction HI and red phosphorous gives
2 6
C H . The
compound (X) is?
Solution: The compound (X) is likely to be alkyne which reacts with water in presence of
2 4
H SO and
4
HgSO as catalyst to form a carbonyl compound. HI and red
phosphorous can reduce a carboxyl compound to alkane having same number of
carbon atoms.
Therefore (Y) is likely to be acetaldehyde which is the hydration product of
ethyne

2 4
4
H SO
2 2 3 HgSO
X
(Y)
HC CH H O [CH CHOH] CH CHO + =

red P
3 3 3 2 2
CH CHO 4HI CH CH 2I H O + + +
Problem 6: What is the major product by the addition of HCl to 2, 2, 2-trichloropropene?
Solution:
3
CCl is a strongly electron withdrawing group. The addition of HCl to >C=C<
double bond of 2, 2, 2-trichloropropene does not follows the Markownikoffs rule
because intermediate secondary carbonium ion is destabilized by the 1 effect of
3
CCl group.

H
3 2 3 3
Less stable
CCl CH CH CCl CHCH
+
+
=
Instead the addition follows anti markownikoffs rule because primary carbonium
ion becomes relatively more stable.

H Cl
3 2 3 2 2 3 2 2
relatively more
stables
CCl CH CH CCl CH CH CCl CH CH Cl
+
+
=
Problem 7: Write equation showing how the following compound can be converted to (a) an
epoxide (b) a diol (c) a ketone.
which on treatment with alc. KOH and aq. KOH separately gives (A) and (C) respectively. (C)
can also be obtained by heating calcium salt of 2-methyl propanoic acid with calcium
acetate. What are (A), (B) and (C)?
Problem 8: Identify (A), (B) and (C) in the following reactions

3
3
4
HCO H
CrO
in AcOH
aq. KMnO
excess
(A)
(B)
(C)

CH
3
1 eqv.

Solution: i) Peroxy formic acid hydroxylates double bond but not triple bond. Therefore,
compound (A) is
CH
3
O H
OH

ii) Oxidation of triple bond is very much slower than that of double bond.
Therefore, by using a suitable oxidizing agent it is possible to selectively
oxidize double bond in presence of triple bond.
3
CrO in presence of AcOH is
one such oxidizing agent, which oxidizes double bond and not triple bond.
Thus, compound (B) is

HOOC
CH
3
COOH

iii) Aqueous
4
KMnO hydroxylates both the double bond as well as triple bond.
The compound (C) is

OH
O H
C
O
C
O
CH
3

Problem 9: Write down the structures of close homolooguoes of heptane having in their
molecule one quaternary carbon atom and the other having two tertiary carbon
atom.
Solution: Homologuoes of heptane (C
7
H
16
) are hexane (C
6
H
14
) and octane (C
8
H
18
).
CH
3
CH
3
C H
3
CH
3
2,2-dimethylbutane
C H
3
CH
3
C H
3
CH
3
2,2-dimethylhexane
C H
3
C H
3
CH
3
CH
3
2,3-dimethylbutane
C H
3
C H
3
CH
3
CH
3
2,3-dimethylhexane
Quaternary carbon
t t t t

Problem 10: Which alkane, having a molecular weight of 86, will form only two monobromo
alkanes?
Solution: General formula of alkane is C
n
H
2n+2
. Its molecular weight = 86
12n + 2n + 2 = 86
n = 6
Hence the given alkane is C
6
H
14
.

Its isomer
C H
3
C H
3
CH
3
CH
3
would give two products


C H
3
C H
3
CH
3
CH
3
2
Br / UV light

Br
C H
3
CH
3
CH
3
CH
3
+
C H
3
C H
3
CH
3
Br

Problem 11: A hydrocarbon (A) was found to have a vapour density of 36. It forms only a
single monochloro product. What is (A)?
Solution: Molecular weight = 2 VD = 2 36 = 72
C
n
H
2n+2
; 12n + 2n + 2 = 72, n = 5
The alkane is C
5
H
12
; its isomer neopentane has all the four identical H, hence will
give only one monochloro product.

CH
3
CH
3
CH
3
C H
3

Problem 12: Write balanced equations, naming all organic products, for the following
reactions;
a) isobutyl bromide + Mg/ether b) t-butyl bromide + Mg/ether
c) product of (a) + H
2
O d) product of (b) + H
2
O
Solution: a)
ether
Mg +
CH
3
H
C H
3
Br
CH
3
H
C H
3
MgBr

b)
ether
Mg +
Br
CH
3
CH
3
C H
3
MgBr
CH
3
H
C H
3

c)
2
H O +
CH
3
H
C H
3
MgBr
CH
3
C H
3
C H
3
isobutane
Mg(OH)Br +

d)
2
H O +
MgBr
CH
3
H
C H
3
CH
3
C H
3
C H
3
isobutane
Mg(OH)Br +

Problem 13: Chlorination of ethane (CH
3
CH
3
) to ethyl chloride is more practicable than the
chlorination of n-pentane to 1-chloropentane. Why?
Solution: It is because monochlorination of ethane gives only ethyl chloride, whereas
monochlorination of n-pentane gives three isomeric monochloro

h
3 3 2 3 2
CH CH Cl CH CH Cl HCl
v
+ +

2
Cl
h
HCl
v

+
C H
3
CH
3
C H
3
Cl
C H
3
CH
3
Cl
+
C H
3
CH
3
Cl

Problem 14: What products are obtained when 1-bromo-2-methyl propane and 2-bromo-2-
methyl propane are allowed to react with metallic sodium in dry ether? Give their
IUPAC names and name the reaction involved.
Solution:
CH
3
CH
3
C H
3
CH
3
CH
3
CH
3
2,2,3,3-tetramethylbutane
CH
3
CH
3
C H
3
CH
3
C H
3
2,2,4-trimethylpentane
C H
3
C H
3
CH
3
CH
3
2,5-dimethylhexane

It is Wurtz reaction
Problem 15: A chloro derivative (A) on treatment with Zn-Cu couple gives ahydrocarbon of
five carbon atoms. When (A) is dissolved in dry ether and reacted with Na, the
product is 2,2,5,5-tetramethyl hexane? What is (A)?
Subjective
Problem 1: Devise sequences for preparing the following compounds from benzene:
i)
NH
2
NO
2

ii)
OMe
Br

Solution: i) The process can be started if we can do the nitration to benzene ring two
times and then can reduce one of the group selectively. Ammonium
sulphide allows selective reduction of one nitro group in the presence of
another. The mechanism of this reaction is complex. It is the
transformation itself which you need to know.

NH
2
NO
2
2 4
3
H SO
HNO / A

NO
2
NO
2
4 2
( NH ) S

NH
2
NO
2
Target

ii) The target can be achieved if we can form phenol from benzene.
Formation of phenol from benzene is not straight forward. The route
shown below involves the nitration, reduction to the aniline and
diazotization. Hydrolysis of the diazonium ion gives phenol.

OMe
Br
2 4
3
H SO
HNO

NO
2
Sn / HCl

NH
2
Target
2
2
HNO
H O(warm)

OH

The next steps involve temporary introduction of a SO
3
group as a
protecting group of the para-position. This allows selective bromination of
the ortho-position. (note: which products would you get without the SO
3

group?)
OMe
2 4
Me SO / NaOH

2 4
H SO
A

OMe
SO
3
H
2 3
3
i) Br ,FeBr
ii) H O ,
+
A

OMe
Br

Problem 2: Show the exact structure of the product (or products) of each EAS reaction
below. State whether each reaction is expected to be faster or slower than the
corresponding reaction of benzene
i)
3
2 4
HNO
H SO

ii)
3
2 4
HNO
H SO

O

iii)
2
Br

O

iv)
2
3
CH Cl
AlCl

CN
O
CH
3


Solution: i)
O
2
N
+ NO
2

each phenyl group acts as an activating ortho/para director to the other
(equivalent) ring. This reaction would be faster than the nitration of
benzene.
ii)
O
NO
2

The carbonyl group acts as a deactivating meta director to both
(equivalent) rings. This reaction will be slower than the nitration of
benzene.
ii)
+
O
Br
O
Br

The oxygen containing ring can be viewed as an OR group and an R
group attached to the benzene ring. Although both groups are activating,
the OR group is more strongly activating, so the position ortho and para to
it will be brominated. This reaction will be faster than the bromination of
benzene, which requires a catalyst.
iv)
CN
O
CH
3
CH
3

The reaction will be faster than that of benzene because of the activating
nature of OCH
3
group which will be dominating over the deactivating
group CN.
Problem 3: The
3 3
N(CH )
+
and CN substituents are both meta directors. Still nitration of
the corresponding benzene derivative does give a minor amount of the ortho
and para isomers of the product. Which of the two substituents should lead to
a greater ortho/para ratio? Why
Solution: The CN group, being a linear two atom group, is much less sterically
demanding than the t-butyl like
3 3
N(CH )
+
group. So, the CN group should
give greater ortho/para ratio. In fact, here are the actual data:
Group % Meta % Ortho % Para Ortho/para ratio
3 3
N(CH )
+

87 2 11 0.18
CN 81 17 2 8.5
Problem 4: Suggest a multi step synthesis for each of these compounds, starting with
benzene and any other reagents you need. Indicate with an asterisk each step
where a separation of positional isomers might be necessary.
i)
CO
2
H
NO
2
(three steps)

ii)
Br
Br
(six steps)

Solution: i) Since we start with benzene and ultimately generating the para isomer of
the product, we must at some point perform an EAS reaction with an
ortho/ para director already in place. Unfortunately, both -CO
2
H and -
NO
2
are meta directors. So, one or the other must have arisen from ortho /
para director during the synthesis. The only way we have seen so far to
make a -CO
2
H group involves KMnO
4
oxidation of an alkyl group, which
is an ortho / para director! Therefore, a logical synthetic sequence would
be

CH
3
CH
3
NO
2
CO
2
H
NO
2
* Separate para isomer from ortho (and some meta)
3
3
CH Cl
AlCl

3
*
2 4
HNO
H SO

4
2
KMnO
H O

If we had nitrated first, then alkylated and oxidized, the meta isomer
would have been the predominant product.
ii) Since we generate the meta isomer in this case, we need to perform an
EAS at some point with a meta director already in place. But both groups
on the ring are ortho / para directors. Let's see if we can devise a logical
sequence using "retro" (backward) synthetic analysis, one that involves a
meta director ultimately transformed into an ortho / para director. The
logical last step in the synthesis would be benzylic bromination.

Br
CH
3
Br
CH
3
Br
NBS
In

The meta bromine could arise via diazotization of the corresponding
amine which, in turn, could result from reduction of a nitro group (a meta
director)

Br N
2
NH
2
NO
2
CuBr

2 HNO
H
+

2 H
cat.

Now, all we have to do is alkylate nitrobenzene. Unfortunately, Friedel
alkylations of deactivated ring usually fail because the catalyst coordinates
to the electron - withdrawing substituted rather than the alkyl halide. To
avoid this problem, the alkylation can be performed as follows:

NO
2
NO
2
3 2
2 4
CH CH OH
H SO

3
2 4
HNO
H SO

In the case, the H
2
SO
4
catalyst protonates the OH group ethanol, resulting
in the transfer of "CH
3
CH
2
+
" to the meta position of the ring.
Problem 5:
3
HF or BF
A
C H
3
CH
2

Identify A and also the electrophile involved in the reaction.
Solution:
H
+

C H
3
CH
2
C H
3
CH
3

+
C H
3
CH
3
CH
3
C H
3
(A)

A is iso propyl benzene (cumene) and electrophile involved is
CH
3

CH

CH
3
(Isopropyl carbocation). Rearrangements are also possible
in Friedel Crafts, reactions when benzene is treated with n-butyl chloride and
Lewis acid the product obtained is isobutyl benzene.
Problem 6: What happens when benzene is treated with methyl chloride in presence of
anhydrous AlCl
3
and the product is treated with excess of chlorine in presence
of UV light?
Solution: 2 2
3
2
6 6 3 6 5 3 6 5 2 6 5 2
Benzene
6 5 3
Benzotrichloride
anhy. Cl Cl
AlCl UV light
Cl
C H CH Cl C H CH C H CH Cl C H CHCl
C H CCl
+

Problem 7: Complete the following
a)
+
CH
2
C H
3
C H
3
3
BF
?

b)
+
3
AlCl
? C H
3
Cl
C H
3

c)
2 5
C H OH
Na
?
OH

d)
2
Br
?

Solution: a)
+
CH
2
C H
3
C H
3
3
BF

CH
3
CH
3
C H
3

b)
+
3
AlCl
C H
3
Cl
C H
3
C H
3
CH
3
H

c)
2 5
C H OH
Na

OH O

d)
2
Br

H Br
H Br

Problem 8: Compounds (A), (B) and (C) are three methyl isomeric derivatives of
benzene. Identify which is o-, m- or p- from the products of nitration?

3
2 4
conc. HNO
H SO
A two mononitro product

3
2 4
conc. HNO
H SO
B three mononitro products

3
2 4
conc. HNO
H SO
C one mononitro product
Solution:
3
2 4
HNO
H SO

+
CH
3
CH
3
o-xylene
CH
3
CH
3
NO
2
CH
3
CH
3
NO
2
(A)
CH
3
CH
3
m-xylene
(B)
3
2 4
HNO
H SO

CH
3
NO
2
CH
3
CH
3
NO
2
CH
3
+
CH
3
O
2
N CH
3
CH
3
CH
3
p-xylene
(C)
3
2 4
HNO
H SO

CH
3
NO
2
CH
3

Problem 9:
Starting with benzene and succinic
O
O
O
anhydride synthesise
o-tetralone
O
.
Solution:
+
O
O
O
3
AlCl
FCR

C
O
CH
2
CH
2
C
CH
2
O H
Tetralone o
CH
2
CH
2
CH
2
C
CH
2
O H
2
2
SOCl
SO , HCl

3 2
AlCl / CS
FCR

O
2
Zn Hg conc. HCl
4[H], H O
+

Problem 10: How the following conversions are achieved?
a) C
6
H
5
C
2
H
5
C
6
H
6
b)
C
2
H
5
C
2
H
5

c)
CH
3
C
3
H
7

d)
O
OH

e)
Li


Solution: a)
CH
3
4
KMnO

OH O
Soda lime
A

b)
C
2
H
5
C
2
H
5
3
BF
2 5
2C H OH +

c)
CH
3
Br
CH
3
C
3
H
7
3
3
CH I
AlCl

CH
3
2
Br
Fe

CH
3
Br
+
Separate

CH
3
Br
3 7
2 5 2
C H Br
Na(C H ) O

d)
3
3
CH I
AlCl

CH
3
O
OH
2
Cl
Sunlight

Cl
KCN

CN
2
H O/ H
+

e)
2
Br
Fe

Br
LiBr +
2Li

Li

Problem 11: Predict the structures of the intermediates in the following reaction sequence.

3 3 4
3
i) AlCl H PO Zn / Hg
HCl ii) H O
(A) (B)
+

O
CH
3
+
O
O
CH
3
O
O
O

Solution:
Zn / Hg
HCl

O
CH
3
+
O
O
CH
3
O
O
O
3
3
i) AlCl
ii) H O
+
O CH
3
O
O H
O
3 4
H PO
or HF

(A)
(B)
O CH
3
O H
O
O

Problem 12: Predict the major monosubstituted product in the following cases.
a)
C(CH
3
)
3
CH(CH
3
)
2
3
2 4
conc. HNO
conc. H SO

b)
CF
3
O
2
N
NH
2
2 3
Br AlBr (anhy.) +

c)
Br
CHCl

2
3
OH

d)
OCH
3
CH
3
2 4
H SO
3 2 2
(CH ) C CH + =

Solution: a)
C(CH
3
)
3
CH(CH
3
)
2
NO
2

c)
OH
Br

b)
CF
3
O
2
N
NH
2
Br

d)
OCH
3
CH
3
C(CH
3
)
3

Problem 13: Write the structure of the major product (only monosubstitution is involved in
each case)
i)
+
F
3
AlCl
?
CH
2
Cl

ii)
3
2
AlCl
3 CS
CH COCl ? +
NH C
O
C H
3

iii)
CH
2
2
3
Br
CHCl
?
OH

Solution: i)
F
CH
2
C
6
H
5

ii)
N H C
O
CH
3
O CH
3
CH
3

iii)
CH
2
OH
Br


Problem 14: Hydrocarbon (A) with molecular formula C H
8 8
gave the following reactions:
1. On shaking with bromine, a bromo derivative (B) C H Br
8 8 2
was formed.
2. Vigorous oxidation of the hydrocarbon with alkaline KMnO
4
gave a
monobasic acid (C).
3. Acid (C) on distillation with sodalime gave C H
6 6
. Deduce structures of
A, B and C and name compound (A).
Solution: 1. The molecular formula of (A) and step (3) suggest (A) to be an aromatic
organic compound.
2. Step (2) suggests that (A) has a double bond in side chain. Thus, (A) may
be

CH CH
2
(A) Phenylethene or Vinylbenzene or Styrene

Reaction:
1.
CH CH
2
(B)
Br

2
CHBr
CH
2
Br

2.
CH CH
2
(C)Benzoic acid
Oxidation
alkaline KMnO

4
COOH

3.
Sodalime

COOH
benzene

Problem 15: Describe how mescaline could be synthesized from toluene

O
NH
2
O
C H
3
O
CH
3
C H
3
mescaline

Solution
CH
3
2 4
fu ming H SO
A

CH
3
SO
3
H
SO
3
H
+
i) NaOH,
ii) H
A

CH
3
OH
OH
2 4 3
conc. H SO HNO +

CH
3
OH
OH
O
2
N
2 4
conc. H SO , A
CH
3
OH
OH
O
2
N SO
3
H
NaOH,
H
+
A

CH
3
OH
OH
O
2
N OH
3 2 4 3(CH ) sO NaOH, + A

CH
3
O
O
O
2
N O
C H
3
CH
3
CH
3
2
3 2
1. Sn/HCl
2. NaNO HCl
3. H PO
+
CH
3
O
O
O
C H
3
CH
3
CH
3
4 alk. KMnO , A

O
O
O
C H
3
CH
3
CH
3
3 3 CH Cl AlCl (Excess)
Heat
+

O
O
O
C H
3
CH
3
CH
3
C H
3
2 Cl / hv
O
O
O
C H
3
CH
3
CH
3
Cl
KCN

O
O
O
C H
3
CH
3
CH
3
CN
4 LiAlH

O
O
O
C H
3
CH
3
CH
3
N H
2

LEVEL I

1. Predict the major product in each of the following reactions.

CH
3
O
2
4
1. Br (1 equivalent)
2. NaBH
3. Base
?

2. What would be the major product in following reaction?

2
1 eq.Br / Fe
? N
O

3. When benzene is treated with DCl at low temperatures a compound C
6
H
6
DCl, is
formed. On warming the reactants, C
6
H
6
and DCl are re-formed. However, in the
presence of AlCl
3
an isomer of C
6
H
6
DCl(D) is produced, which on warming, gives
mainly C
6
H
5
D and HCl. Explain
4. Give structure of the principal organic products expected from mononitration of
a) o-nitrotoluene b) m-dinitrobenzene
c) m-cresol d) m-nitrotoluene
5. Account of the following

h
2
1 eq. Br
v
+
Ph
CH
3
C H
3
Ph
CH
3
Br
C H
3

with little or no PhCH
2
C(Br)(CH
3
)
2
formed.
6. C
7
H
7
Cl has four isomers A
1
, A
2
, A
3
and A
4
A
4
A

, e lim Soda ) II
4
KMnO ) I
Benzene, Identify A
1
, A
2
, A
3
and A
4
.
7.
alc. KOH HBr
heat
A B
H
5
C
6
CH
3
Br

8. Oxidation of toluene by acidic KMnO
4
gives poor yield of benzoic acid while oxidation
of p-nitrotoluene gives good yield of p-nitrobenzoic acid. Why?
9. What happens when p-xylene is treated with concentrated sulphuric acid and the resultant
product is fused with KOH?
10.
3 2 4
conc. HNO conc. H SO

CH
3
NO
2

In the above reaction which product is most likely to be formed?

LEVEL II

1. Give the products of the following reactions
a)
2
Br +
N

b)
CH
3
2
+
1. NBS/
2. Mg/Et O
3. ethylene oxide
4. H
A

c)
F
F F
3
anhy.FeCl
2
Cl +


2. An aromatic compound A (C
7
H
7
NO
2
) on reduction gives B (C
7
H
9
N). Diazotization of B
and subsequent treatment with CuCN/KCN gives C (C
8
H
8
O
2
). Hydrolysis of C followed
by oxidation forms D, which has equivalent mass of 83g eq
1
. D forms only one mono
substitution product. Give structure for A, B, C and D.
3. A compound (C
8
H
10
O) upon treatment with alkaline solution iodine gives a yellow
precipitate. The filtrate on acidification gives a white solid E (C
7
H
6
O
2
). Write the
structures of D, E and explain the formation of E.
4. Give the product(s) obtained from the reaction each of the following compounds with
Br
2
/FeCl
3
.
a)
O

b)
O C H
3
NO
2

5. Write the structures of the compounds from the following data.
a)
4 4
hv alc. KOH cold dil hot
2 KMnO KMnO
Br (A) (B) (C) (D) +
Ph
CH
3

b)
HBr
2 3 peroxide
Br FeBr (anhy.) (E) (F) + +
Ph
H CH
3
H

6.
3
AlBr
2
Br
A
+
CH
3
C H
3
CH
3
Br
CH
2
C H
3
C H
3
+ HBr +

7. Compounds (A) and (B) are isomers having the formula C
8
H
10
. On oxidation (A) gives
benzoic acid while (B) gives phthalic acid which forms an anhydride (C) on heating.
Identify (A), (B) and (C).
8. How will you synthesize

CH
3

from benzene?
9. Identify A to C in the following:

4 4
alkaline KMnO LiAlH conc. HCl
ZnCl,
A B C
A

CH
3

10. Complete the following reactions:
a) 4-bromo-2-methylphenol treated with 2-methylpropene and sulphuric acid.
b) p-cresol treated with propanoyl chloride and aluminium chloride.
c) 2,5-dichlorophenol reacts with chlorine in acetic acid.
LEVEL - I

1.
O

2.
N
O
Br



3. Since D is not incorporated into the benzene ring in the absence of AlCl
3
, isomer C has
no C D o bond. Instead, the D end of DCl is attracted to the t cloud of benzene to form
a loosely bound t complex, indicated by an arrow in the structural formula. t complexes
are also called charge transfer complexes, because the electron rich benzene ring, the
donor molecule, transfers some electron density to the electron-poor D of DCl, acceptor
molecule. With the catalyst AlCl
3
, exchange of D
+
for H
+
occurs on warming. This
exchange requires the formation of a C D bond to give the o complex. with D
+
. The
benzene ring is reformed by losing an H rather than the D because the C H bond is
weaker than the C D bond. Notice the delocalization of the positive charge in the o
bond.

complex, C t
6 6
D Cl C H DCl
A
+

4. a)
CH
3
NO
2
NO
2

b)
NO
2
O
2
N NO
2

c)
OH
CH
3
NO
2

d)
CH
3
NO
2
O
2
N

5.
Br
Ph
CH
3
C H
3
Ph
CH
3
C H
3
and
Ph
CH
3
C H
3
2 benzylic 3 alkyl
2
Br / hv

Br
Ph
CH
3
Br
C H
3
Ph
Br
C H
3
CH
3
(major)
(little yield)

This reaction proceeds via free radical mechanism forming 2 free radicals, of which 2
benzylic free radical is stabilized more by resonance of phenyl ring and with
hyperconjugation of CH
3
group, thus resulting in the formation of PhCH(Br)CH(CH
3
)
2

as the major product.
6. A
1
, A
2
, A
3
are o, p, m-chlorotoluenes A
4
- benzyl chloride
7.
A =
H
5
C
6
CH
3

B =
H
5
C
6
CH
3
Br

8. Oxidant is an electrophile, it can attack and destroy the ring in case of toluene. But in p-
nitrotoluene, the NO
2
group deactivates the electrophilic attack on benzene nucleus and
thus increases the yield of p-nitrobenzoic acid.
9.
CH
3

2 4
conc.
H SO

CH
3

CH
3

fusion
with KOH

CH
3

OH
p-Xylene
CH
3

SO
3
H
CH
3

2-5,Dimethylphenol

10.
CH
3
O
2
N
NO
2

LEVEL - II

1. a)
2
Br +
N
N
Br
+
N
Br
Br
(minor)
(major)

b)
CH
3
2
+
1. NBS/
2. Mg/Et O
3. ethylene oxide
4. H
A

OH

c)
F
F F
3
FeCl
2
Cl +
F
F F
Cl


2.
A =
C H
3
NO
2
1-methyl-4-nitrobenzene

B =
C H
3
NH
2
p-toluidine


C =
C H
3
OH
O
4-methylbenzoic acid

D
=
O
O H OH
O
terephthalic acid

3. The reaction of C
8
H
10
O with alkaline solution of iodine is an iodoform reaction. This
reaction is possible if the compound D has CO
2
CH
3
or CH(OH) CH
3
group. The
high carbon content in D indicates that D is an aromatic compound containing a benzene
ring. To account for the given formula, the compound D may be C
6
H
5
CH(OH)CH
3
. The
given reactions are

[O]

H
+
OH
CH
3
O
CH
3
2
I / NaOH

1-phenylethanol
O
O Na
I
I
I
O
OH
benzoic acid
+

4. a)
O Br

b)
O C H
3
Br
NO
2

5. a)
A =
H
5
C
6
Br
C H
3

B =
H
5
C
6
C H
3


C =
H
5
C
6
OH
C H
3
OH

D =
C
6
H
5
O
OH
C H
3
OH
O
+

b)
E =
H
4
C
6
H CH
3
H
p-Br

F =
C
6
H
4
CH
3
Br p-Br

6. The Friedel-Crafts alkylation can be reversed especially when a 3 alkyl group such as
Me
3
C is present. Dealkylation is effected with Alr
3
by transfer of Me
3
C
+
to another arene
used as solvent, or at high temperature by protonation as H
+
and loss of Me
3
C as
Me
2
C = CH2.

+
Br +
CH
3
C H
3
CH
3
CH
3
C H
3
CH
3
H
Br
A

Br
CH
2
C H
3
C H
3
+ HBr +

7.
CH
3
CH
3
CH
3
(A) is
[O]

2
H O
A

(while (B) is
CH
3
CH
3
(B)
O O H
OH
O
O
O
O
CH
3
[O]

OH
O
(C)

8.
+
C H
3
O
Cl
3
AlCl

O
CH
3
Zn(Hg) / HCl
(Clemmensen reduction)

CH
3

9.
A =
OH
O

B =
OH

C =
Cl

10. a)
2 4
H SO

OH
CH
3
Br
+ C H
3
CH
2
CH
3
OH
CH
3
Br
C H
3
C H
3
CH
3

b)
3
AlCl

OH
CH
3
+
OH
CH
3
O
CH
3
C H
3
O
Cl

c)
2
3
2Cl
CH COOH
+

Cl
Cl
OH
Cl
Cl
OH
Cl Cl

Subjective
Problem 1: I t required 0.70 gm of hydrocarbon (A) to react completely with 2 gm Br
2
. On
treatment of (A) with HBr, it yielded monobromoalkane (B). The same compound (B)
was obtained when (A) was treated with HBr in the presence of peroxide. Write down
the structural formula for (A) and explain the reactions involved.
Solution: i) (A) gives monobromoalkane (B) (A) is alkene
ii)

(A)
1 mole
C = C + Br
2
C C
Br Br

Since 2 gm Br
2
reacts completely with = 0.70 g of (A)
160 gm Br
2
reacts completely with =
0.70 160
2

= 56 gm of (A)
Molecular weight = 56
C
n
H
2n
= 56 (since compound is alkene)
12n + 2n = 56
n = 4
Hence (A) is C
4
H
8

iii) Since compound A gives same mono bromoderivative either in presence or absence
of peroxide hence A should be symmetrical alekene.
Hence A = CH
3
CH = CHCH
3
.
Problem 2: (CH
3
)
3
CBr
2
H O
S 1
N
(CH
3
)
3
COH ------------ (1)
(C
6
H
5
)
3
CBr
2
H O
S 1
N
(C
6
H
5
)
3
COH --------- (2)
Equation (1) show no effect with the addition of Br

to the reaction but equation (2)

shows common ion effect if Br

is supplied from external source. Why is

it so?
Solution: Both the reactions followed the formation of carbocation. In the first reaction the
carbocation formed is (CH
3
)
3
C
+
and in second it is (C
6
H
5
)
3
C + needless to say that second
carbonium ion is much more stable than first one. or the carbonium ion is highly reactive
compared to second since (C
6
H
5
)
3
C
+
is more stable reversible reaction would take place


(CH
3
)
3
CBr
(CH
3
)
3
C
+
+ Br

fast
O H
2
(CH
3
)
3
COH + H
+



(C
6
H
5
)
3
CBr
(C
6
H
5
)
3
C
+
+ Br

(stable)
H
2
O (not so fast)
(C
6
H
5
)
3
COH + H
+


and since second reaction involves equilibrium it shows common ion effect in first
reaction in there is no equilibrium it is free from the concentration of Br

.
Problem 3: Alkyl halides are hydrolysed to alcohol very slowly by water, but rapidly by silver oxide
suspended in boiling water.
Solution: RX + Ag
+
[RXAg]
+

[RXAg]
+

Slow
R
+
+ AgX
R
+
+ OH

ROH
Heavy metal ions, particularly silver ions, catalyse S
N
1 reaction and mechanism involves
a fast pre- equilibrium step (the silver ions has an empty orbital).
Problem 4: What happens when ()2 bromooctane is allowed to react with sodium hydroxide
under S
N
2 conditions.
Solution:

C
6
H
13

H
H
3
C
Br
NaOH
S
N
2
HO H
H
3
C
() 2 Bromooctane
C
6
H
13

(+) 2 Octanol

In Fisher projection the above reaction can be represented as follows:


C
6
H
13

Br
H
CH
3

NaOH
S
N
2
C
6
H
13

Br
HO
CH
3


We see that OH group has not taken the position previously occupied by Br

, the alcohol
obtained has a configuration opposite to the bromide. A reaction that yields a product
whose configuration is opposite to that of the reactant is said to proceed with inversion of
configuration.



C
6
H
13

H
H
3
C
Br
NaOH
S
N
2
HO H
H
3
C
() 2 Bromooctane
C
6
H
13

(+) 2 Octanol

Problem 5:

CBr
OH
High
Concentration

CH
3

H
CO
2

OHC
CO
2

H
CH
3

+ Br

(S)- Bromo propanoate ion (R) Lactate ion
Inversion of configuration
Ag2O
Low concentration of

OH
C
CH3
H
CO2

OH
(S) lactate ion

Retension of configuration
Comment on the following observation
Solution: When (S) 2 Bromopropanoic acid is heated with concentrated OH

, the reaction is
bimolecular and it takes place with the inversion of configuration. It is a simple as it used
to be in normal S
N
2 reaction.
On the other hand in second case with less concentration of

OH and in the presence of

Ag, we are getting the same configuration although it followed second order kinetics.
One of the possible ways is that it undergoes inversion two times. In first inversion (S)
to (R) and again (R) to (S). Infact, it was found to be so. Lets see how it happened.
Actually in this case, the mechanism for the reaction involves the participation of
the carboxylate group, (neighbouring group participation).
In step 1: An oxygen of carboxylate ion attacks the nuelcophilic centre (C) generated
because of the removal of Br

in the form of AgBr precipitate and in this step involves

first inversion of configuration.


Br
C
C
O
O

H
Ag
+

C
C
O
O
H
CH
3

Br

Ag
+

C
C
O
O
CH
3

H
+ AgBr
(first inversion)

Step:2: Now since this 3-membered ring is highly strained it used to get opened as the
H
2
O molecule approaches it. The water molecule reacting will attack from the back side
of the ring and hence this also results in the inversion of configuration, resulting two
inversion or the retention of configuration.


C
C
O
O
H
CH
3

OH
2

+o
o
C
C
O
O
H
CH
3

OH
2

OC
C
O
H
CH
3

OH
+ H
+

(second inversion)

The net result of the two steps or two inversion is the retention of the configuration
Problem 6: An olefinic hydrocarbon (A) adds chlorine to give a compound (B) which when treated
with sodamide gives a hydrocarbon (C). (C) is treated with dilute H
2
SO
4
in the presence
of mercuric sulphate and then (D) is obtained. (D) on reaction with alkaline
hypochlorite gives an acid (E). (D) on reduction with LiAlH
4
gives (F) which on
dehydration with alumina gives a hydrocarbon (G) which is isomeric with (A) and
which on ozonolysis gives two moles of acetaldehyde. How do you account for these
reactions?
Solution:
2 2 2 4
2
Cl NaNH dil. H SO Alkaline Hypochlorite
Hg
Alkene Acid
(A) (B) (C) (D) (E)
+

Ozonolysis Dehydration
3
Alumina
Isomeric with
(A)
2CH CHO (G) (F)

i) (D) reacts with alkaline hypochlorite to form carboxylic acid hence (D) must be
methyl ketone.
ii) (G) on ozonolysis gives two moles of CH
3
CHO hence (G) must be
2-Butene
iii) 2-Butene (G) is obtained by the dehydration of (F) hence (F) must be butan-1-ol or
butan-2-ol.
iv) (F) is obtained by reduction of (D) methyl ketone. Hence (F) is definitely a secondary
alcohol (Butanol-2)
(A) is isomeric with (G) Hence (A) is butene-1 (from the above sequence of reactions it
could not be isobutene)

2
Cl

C H
3
CH
2
C H
3
Cl
Cl
2
NaNH
C H
3
CH
C H
3
CH
3
O
hypo
chloride
C H
3
OK
O
3
2
O
3
H O
2CH CHO C H
3
CH
2
2 3
2
Al O
H O
C H
3
CH
3
OH
2
2 4
Hg / H SO
+
4
LiAlH
(A)
(B)
(G)
(F)

Problem 7: A hydrocarbon (A) of molecular weight 54 reacts with excess of Br
2
in CCl
4
to give a
compound (B) whose molecular weight is 593% more than that of (A). However on
catalytic hydrogenation with excess of hydrogen (A) forms (C) whose molecular weight
is only 7.4% more than that of (A). (A) reacts with CH
3
CH
2
Br in the presence of
NaNH
2
to give another hydrocarbon (D) which on ozonolysis yields diketone (E). (E)
on oxidation gives propanoic acid. Give structures of (A) to (E) with reasons.
Solution:
Compound (A)
Molecular weight 54
2 4
Br / CCl
excess

Compound (B)
Molecular weight
(593% more than A)
(D)
Diketone (E)
Diketone (E)
O
3
CH
3
CH
2
Br
in NaNH
2
(O)
Catalytic
Hydrogenation
(C)
Molecular weight 7.4% of (A)

100 gm of (A) add Br
2
and the new weight is 593 gm
54 gm of (A) add Br
2

and the new weight is
593 54
100

= 320.2 gm
No. of moles of Br
2
=
Weight 360.2
Molecular weight 160
= = 2 mole
i) As two moles of Br
2
adds hence compound has two t bonds hence general formula
should (C
n
H
2n2
)
C
n
H
2n-2
= 54
12n + 2n 2 = 54
n = 4 molecular formula = C
4
H
6

ii) (A) reacts with CH
3
CH
2
Br in presence of NaNH
2
Compound (A) should be
terminal alkyne i.e. 1-butyne

CH
3
CH
2
Br
in NaNH
2
(O)
Catalytic
Hydrogenation

(A)
C H
3
CH
2
4
Br
CCl
C H
3
Br
Br
Br
Br
C H
3
C
2
H
5
O
3
C H
3
C
2
H
5
O
O
3 2
2CH CH COOH
C H
3
CH
3
(C)
(D)

Problem 8: A hydrocarbon C
8
H
10
(A) on ozonolysis gives compound C
4
H
6
O
2
(B) only. The
compound (B) can also be obtained from the alkyl bromide C
3
H
5
Br (C) upon treatment
with magnesium in dry ether followed by CO
2
and acidification. I dentify (A), (B) and
(C) and also give equations for the reactions.
Solution: i) (C) is an alkyl bromide C C t bond is absent in it.
ii) Molecular formula (C
3
H
5
Br) (C) shows (C) would be a cyclic compound

Br

iii) CO
2
and on acidification would give carboxylic acid compound (A) would be
symmetrical alkyne (B) is obtained by ozonolysis of (A) C
8
H
10
.


Br
ether
Mg

MgBr
O H ) ii
CO ) i
3
2

O
||
C OH
ozonolysis

C C
Cyclopropyl
bromide
Cyclopropane
carboxylic acid
Dicyclopropyl
acetylene
(A)
(B)
(C)

Problem 9: How would you synthesize CH
3
CH
2
C CH from CH
3
CH
2
I
Solution: a) What are the connectivities of the two compounds? How many carbon atom does
each contain? Are there any rings? What are the position of branches and functional
groups on the carbon skeletons?
The starting material has a two-carbon chain, an ethyl group, with an iodine atom
bonded to one carbon. The product has a four-carbon chain in which the two carbons
that have been added to the ethyl group are bonded to each other by a triple bond.
b) How do the functional groups change in going from starting material to product?
Does the starting material have a good leaving group?
The iodine atom in the starting material is a leaving group and has been replaced in
the product by an alkyne functional group.
c) Is it possible to dissect the structures of the starting material and product to see which
bonds must be broken and which formed?

Bond to be broken
C H
3
CH
2
I
C H
3
CH
C H
3
CH
2
CH C
new bond to be formed
the pieces that have to be brought together

d) New bonds are created when an electrophile reacts with a nucleophile. Do we
recognize any part of the product molecule as coming from a good nucleophile or an
electrophilic addition?
The ethyl group is attached to a leaving group in the starting material and so must
serve as the electrophilic center. A check reminds us that the
CCH group is related to the nuclophile HC C:

, the conjugate base of an alkyne.

e) What type of compound would be a good precursor to the product?
A displacement of the iodine atom by the nucleophile will give us the product we
want.

C H
3
CH
2
I
+
o
C H
3
CH
C CH I

f) After this last step, do we see how to get from starting material to product? If not we
need to analyze the structure obtained in step 5 by applying questions 4 and 5 to it.
These steps are a restatement of the way of thinking about problems. It will be
helpful to you to ask yourself these questions in a systematic way for each problems
you work, on until this way of thinking becomes familiar and easy.
Problem 10: Predict the product(s) of the reaction.

C H
3
Br
S
-
Na
+
+

a) To what functional group classes do the reactants belong?
b) Does either reactant have a leaving group?
c) Are any of the reactants acids, bases, nucleophiles, or electrophiles?
d) What is the most likely first step for the reaction? Most common reactions classified
as either protonation deprotonation reactions or reactions of a nucleophile with an
electrophile.
e) What are the properties of the species present in the reaction mixture after this first
step? Is any further reaction likely to occur?
Solution: a) One reactant is an alkyl halide, the other is a sulfur anion (remember that sodium ions
are usually spectator ions, they are to balance charge but not to participate in the
reaction).
b) Yes, the bromine atom in 1-brompropane is a leaving group.
c) The sulfur anion is a nucleophile. The alkyl halide contains an electrophilic carbon
atom.
d) No strong acids (pK
a
< 1) or bases (pK
a
of conjugate acid > ~13) are present this
reaction mixture so a protonation-deprotonation reaction is not probable. Reaction of
the nucleophilic sulfur atom with the electrophilic carbon atoms is most likely.

C H
3
Br
S
+
+
o
C H
3
S
Br

o

e) All species formed are stable. No further reaction will occur. The complete equation
is:

C H
3
Br
S
-
Na
+
+
C H
3
S
+
Na Br +

Problem 11:
Comment on the following observation
Br
C
C H
3
H
OH
High concentration
O H
CO
2
CH
3
H
Br +
O
2

Retention of configuration
Solution:
(S) Bromopropanoate ion (R) Lacate ion
Inversion of configuration
CO
2
OH
H
C H
3
(S) lacate ion
2
Ag O
-
Low concentration of OH

Problem 12: Explain the fact that a small amount of NaI catalyzes the general reaction
RCl +RO

Na
+
ROR' +NaCl
Solution: With I

the overall reaction occurs in two steps, each of which is faster than the
uncatalysed reaction.
Step 1: RCl + I

RI + Cl

This step is faster because I

, a soft base has more nucleophilicity than OR

, a hard base
Step 2: RI + R'O:

ROR' + I'
This step is faster because I

is a better leaving group than Cl

Problem 13: i)
CH
3
CH
2

ii)
C H
3
CH
2
C H
3
NH
2

iii)
C H
3
CH
2
C H
2
CH
2

Solution: i)
CH
3
2
Br
hv

CH
3
Br
alc. KOH

CH
2

ii)
C H
3
CH
2 C H
3
NH
2
2 2
HBr
H O
C H
3
Br
3
NH

iii)
C H
3
CH
2 C H
2
CH
2
2
Br / h
alc. KOH
v

Problem 14: I dentify A to D in the following sequence of reactions.

3 2
O / H O/ Zn
3
CH CHO D
aq. NaOH oxidation NaOI
4 9 4 10 4 8
(A) (B) (C)
C H Br C H C H O yellow ppt.
A

2 4
conc. H SO Tollens' reagent
no reaction

Solution:
A =
C H
3
CH
3
Br

B =
C H
3
CH
3
OH

C =
C H
3
CH
3
O

D =
C H
3
CH
3

Problem 15: I dentify A to E in the following

3
3
CH MgBr
H O
A
+

3 2 2 3 2
CH CH CH Cl / AlCl aq. NaOH/I H soda lime
B C E
+
A A

Ph CH
3
CH
3
OH

Solution:
A =
CH
3
O

B =
ONa
O


C =
OH
O

D =


E =
CH
3
CH
3