Shri Bapu R.

Thorat
Assit. Professor of Chemistry
Govt. of Maharashtra,

Ismail Yusuf Arts, Science and Commerce College, Jogeshwari (E),

Maharashtra 400060

The major product formed in the reaction of 2-methylbute-3-ene-2-ol with HBr

Br

H3C
2.

1.
H3C

CH3

Br
OH

3.

H3C

H3C

CH3

4. H3C

H3C
CH3

CH3

Br
O

Br

H3C
CH2
H3C

OH
2-methylbut-3-en-2-ol

HBr

H3C

H3C
CH2

CH3

HBr

H3C

H3C

CH3

CH3

H3C

HBr

OH

OH
2-methylbut-3-en-2-ol

H3C

H3C

CH

H3C
+

H
H3C

-H2O
+

H
H3C

CH2

H3C

CH3

CH3
C

CH2

CH2

H3C

H3C

H3C
Br-

Br-

CH3

CH3

CH2

H3C

CH3
Br

H3C
Br

Br

The product formed in the reaction given belowCH3

?
CH3

CH3

CH3
1.

2.
CH3

CH3
CH3
3.

CH3
4.

CH3

CH3

Pericyclic Reaction

Electrocyclic reactions-

Process in which two bonds

convert into one & one bond and vice versa.

No.
of Process
electrons
involved

HOMO

Node

Transition
state

Symmetry

03

Aromatic

Axis
symmetry

Photochemical

CH3
CH3
CH3
HOMO, node - 3

of Con rotatory

CH3
h
Con

H3C

Rotation allow

CH3

Which of the following compounds is not aromatic in nature -

A. Cyclopentadienyl anion

C. Fullerene C60

B. Pyrrole

D. Azulene

An aromatic (or aryl) compound contains a set of covalently bound atoms with
specific characteristics:
A delocalized conjugated system, most commonly an arrangement of
alternating single and double bonds
Coplanar structure, with all the contributing atoms in the same plane
Contributing atoms arranged in one or more rings
A number of delocalized electrons that is even, but not a multiple of 4. That is, 4n
+ 2 number of electrons, where n = 0, 1, 2, 3, and so on. This is known
as Hckel's Rule.
A. Cyclopentadienyl anion

C. Fullerene C60

B. Pyrrole

D. Azulene

Choose the correct option as indicated in series given below a

2+

Homoaromatic
+

CH

iii

ii

CH

CH

Aromatic
iii

ii

CH

Non-aromatic

C60
i

ii

A. Homoaromatic i; Aromatic ii; Non-aromatic - iii

B. Homoaromatic ii; Aromatic iii; Non-aromatic - iii
C. Homoaromatic ii; Aromatic ii; Non-aromatic - ii
D. Homoaromatic ii; Aromatic ii; Non-aromatic - iii

iii

An aromatic (or aryl) compound contains a set of covalently

bound atoms with specific characteristics:
A delocalized conjugated system, most commonly an
arrangement of alternating single and double bonds
Coplanar structure, with all the contributing atoms in the same
plane
Contributing atoms arranged in one or more rings
A number of delocalized electrons that is even, but not a multiple of
4. That is, 4n + 2 number of electrons, where n = 0, 1, 2, 3, and so
on. This is known as Hckel's Rule.
Homoaromaticity in organic chemistry refers to a special case
of aromaticity in which conjugation is interrupted by a single
sp3 hybridized carbon atom.

Among the following compounds the one which has highest dipole moment is-

1.

2.

CH3
3.

4.
CH3

Dipole moment is the vector quantity which depends on the magnitude of the
charge and distance between the charge.
=qr

Nonaromatic

Aromatic
rings

CH3
CH3

Nonaromatic

CH3
-

CH3

Consider the following reaction sequence-

OH

OH
70%

OH

90%
Sn/HCl

H2N

O 2N
OH
25%

phenol

OH
90%
Ac2O

AcHN
OH

OH
90%
Sn/HCl

NO 2

90%
Ac2O

NH2

NHAc

The overall yield of for the formation of 2/4-hydroxyacetanilide from the phenol
respectively are approximately.
1. 57 and 20
3. 83 and 68

2. 57 and 68
4. 83 and 20

Suppose initial amount of phenol used for the reaction is 100 g.

For step I, 70 g of p-nitrophenol is available for further reaction while
for step II, 25 g of o-nitrophenol is available for the further reaction.
Step - I
(100 x 70/100) (90/100)(90/100)
= 56.70 %

Step - II
(100 x 25/100) (90/100)(90/100)
= 20.25 %

The stereo chemical notation for the following compound is -

A. 1Z, 3Z, 5E, 7Z, 9Z

B. 1E, 3Z, 5E, 7Z, 9Z

C. 1E, 3Z, 5Z, 7Z, 9Z

D. 1E, 3Z, 5E, 7Z, 9E

(1E,3Z,5E,7Z,9Z)-1-methylcyclodeca-1,3,5,7,9-pentaene

The Cahn-Ingold-Prelog priority rules are used for naming geometric

isomers (e.g. E- or Z-alkenes).
- Higher priority groups are present on the same side of the double bond it is a (Z)alkene (German; zusammen = together).

- Higher priority groups are present on the opposite side of the double bond it is an
(E)-alkene (German; entgegen = opposite)
1. The higher the atomic number of the immediate substituent atom, the higher the priority.
2. Different isotopes of the same element are assigned a priority according to their atomic mass.
3. If two substituents have the same immediate substituent atom, evaluate atoms progressively further
away from the chiral center until a difference is found.
4. If double or triple bonded groups are encountered as substituents, they are treated as an equivalent set of
single-bonded atoms.

Meso-tartaric acid is achiral since:

A. It has a plane of symmetry in both the eclipsed and staggered
conformations
B. It has a center of symmetry in eclipsed conformation and plane of
symmetry in staggered conformation
C. It has a center of symmetry in both the eclipsed and staggered
conformations
D. It has a plane of symmetry in eclipsed conformation and center of
symmetry in staggered conformation

COOH
H

OH

OH

COOH
2,3-dihydroxybutanedioic acid

Eclipsed

Staggered

A plane of symmetry is an imaginary plane that bisects a molecule into halves that are
mirror images of each other.

The center of symmetry i is a point in space such that if a line is drawn from any part
(atom) of the molecule to that point and extended an equal distance beyond it, an
analogous part (atom) will be encountered.

The correct molecule having the absolute configuration as (S)4-bromo-cis-2-pentene is-

A.

H CH3
Br

CH3

B.
H

C.

H CH3
Br

Br CH3
H
H

CH3

H
CH3

D.

Br CH3
H
H

CH3
H

H
A.

H
Br

CH3
H

Br

CH3

B.

H
CH3
(2E,4S)-4-bromopent-2-ene

C.

CH3

Br CH3
H
H

H
H
(2Z,4S)-4-bromopent-2-ene
Br CH3
H

D.

CH3

(2E,4R)-4-bromopent-2-ene

CH3
H

(2Z,4R)-4-bromopent-2-ene

The symbol R comes from the Latin rectus for right, and S from the Latin sinister for left.
Lowest Priority
group away from
viewer

identify the chirality

center(s)

assign the relative priorities

rotate the low priority group

away

determine the sense of groups 1 ->

3
clockwise = R

The product in the following reaction is:

Ph
OH
N

PCl5

H3CO
O

Ph

NHPh
N
O

A.

B.
H3CO

H3CO
Ph
O
C.
H3CO

D.

Beckmann rearrangement
Syn
3. Catalyzed by phosphorous pentachloride
Cl
Cl
P
Cl
Cl
R''
R''
OH PCl
O+ H
5
N
N
R'
R'

Cl

OH2

N
R''

R'

HO
R''CO-NHR'

N
R''

R'

Anti

In aldoxime, H and OH are on same side called syn and are

opposite side of plane are called anti. In case of ketoxime,
configuration can be determined by using priority rule, if same
priority group present on same side is syn and are opposite called as
anti.
Beckmann rearrangement is highly stereospecific, the group which
is anti with respect to OH group of oxime migrates.

The intermediate involved in the Hofmann rearrangement is:

A. Amine

B. Acid

C. Isocyanide

D. Acid
Chloride

The rearrangement which converts an amide into amine with one carbon atom less
by the action of alkaline hypohalide or bromine in alkali is known as Hofmann
rearrangement/reaction.

R-CONH2

Br2

+ 4 KOH

R-NH2 + 2 KBr + K2CO3 + 2 OH

2

O
R-CONH2 +

KOH

+ Br2

KOH

O
R

N Br
H

N Br

Nitrene
O

R-NH2 + CO2
primary-amine

R N
H
H
carbamic acid

OH2

R N
O
Isocyanide

The Stobbe condensation is treatment of ketone or aldehyde in presence of base

with-

A. Anhydride

B. Diester
C. Aldehyde
Perkin condensation

D. Ketone

Aldol condensation

Stobbe condensation

Perkin reaction

Aldol condensation

The following reaction is an example of

NaOCH3/CHCl3

work up with water

A. Mannich Reaction

B. Vilsmeier-Haack Formylation
C. Fridel-Craft reaction
D. Reimer-Tiemann reaction

N
H

CHO

Mannich reaction

Vilsmeier Haack reaction

FriedelCrafts reaction

Reimer Tiemann reaction

The product of the following reaction isO

i. MeMgBr

Cl
ii. H2O

HO

CH3

HO

CH3

B.

Cl

A.

C.

HO

CH3
CH3

D.

H
CH3

Grignard Reagent Reactions

Grignard reagent is used for the synthesis of Ketone and alcohol. Ketones are
synthesised from acid, ester, anhydride, amide and acid halide under control
condition (1:1 proportion) while in presence of excess Grignard reagent, alcohol is
formed but is not stable and undergoes dehydration.
-

O MgBr
CH3

O
Cl

Cl

MeMgBr

CH3

OH
CH3

H2O
-MgBrOH

-MgBrCl

CH2

Cl
+

O MgBr
CH3

O
CH3

CH3
MeMgBr

MeMgBr
-CH4
-MgBrOH
H2O
-MgBrOH

OH
CH3
CH3

O
Zn(Hg)
HCl

H3C

H3C

A. 1-propene

B. Propane

C. Hexane

D. Diisopropyl ether

H3C

H3C

H2SO4

H
O

OH

H3C

-H2O

H3C

-H+

CH

H3C

H2C

HO
CH 3

H+ H2SO4

H 3C

H3C

H3C

-H+

O
H3C

CH3
H3C

H 3C

H
O

H3C

OH

CH3
H3C

H 3C

H3C
+

CH
H3C

Aimless is not Crime

But
Short aim is Crime

H3C

H3C

CH3

H3C

A.

H3C

CH3
OH

H3C
Br

Br
H3C

CH3

KOH

H3C

B.

CH3

H3C
OH

CH3
H3C

C. H C
3

H3C

D.

H3C

CH3

H
H3C

H3C

CH3

H3C

H
H

H3C

Br

CH3 KOH

H3C
H3C

Br

Stable

H
H3C

CH3

CH3

H3C
H

Stability of
alkenes
H
H

CH3

H
H

H
H

H
H

H3C
H

CH3

H
C - H bond

H
H

H
C - C bond
H

Among the choices, the correct statement for A formed in the following reaction -

H3C
H3C

H
O
CH3

A.
B.
C.
D.

H3C
N
H

H3C

A is a single enantiomer
A is racemic mixture.
A is a mixture of two diastereomers
A is a mixture of two epimers

OH

N
CH3

Predict the stereochemical outcome of the following reaction O

LiAlH4

CH3

HO

H
CH3

A.

Non-racemic

OH

HO
CH3

C.
Racemic

CH3

B.

Racemic
H

OH

H
CH3

D.
Non-racemic

With rigid cyclic ketones, the stereochemical preduction of reduction is not eassy. In some cases,
stable equitorial alcohol is obtained as major product while in some reductions, axial alcohol is
main product.
The reagent approach to carbonyl group in an axial direction, equitorial alcohol formed.
The reagent approach to carbonyl group in an equitorial direction, axial alcohol formed.
In hindered ketones, axial approach may be hampered by steric factors and hence equitorial
approach of the reagent is favoured and forming the axial alcohol.

Less hindered side

for LAH attach
O

Hindered side for LAH attach

CH3

CH3
H

MODERN
METHODS
OF
ORGANIC
SYNTHESIS
by

LiAlH4
LiAlH4

OH
CH3

Attack of LAH from less hindered side

(Major)

HO

Page.no. 441

H
CH3

Attack of LAH from hindered side of CH 3

The mass spectrum of a halogen containing compound showed M+ and M+ + 2 of

equal intensity. Therefore, the compound contains -

A. Bromine

B. Chlorine

C. Iodine

D. Fluorine

Natural Abundance of element

3:1

1:1

Fluorine
Iodine

18.99 (100%);
126.9 (100%).

In Shapiro reaction, using 2-octanone, [p-tolunesulfonylhydrazone of 2octanone treated with CH3Li], the product obtained is:

A. 1-Octene
B. (E)-2-octene

C. (Z)-2-octene

D. (Z)-3-octene

The conversion of ketone p-toluenesulfonylhydrazones to alkenes takes place on

treatment with strong bases such as an alkyllithium or lithium dialkylamide. This is
known as the Shapiro reaction.
The reaction proceeds through the anion of a vinyldiimide, which decomposes to a
vinyllithium reagent. Contact of this intermediate with a proton source gives the less
substituted alkene.

1-Octene is the exclusive product from 2-octanone

The correct reagent combination / reaction sequence for effecting the following
conversion is -

O
OH

A.

(a) Me3SiCH2OCH3, nBuLi, (b) H3O+, (c) NaBH4, MeOH

B.

(a) Ph3PCH2OCH3. HCl, nBuLi, (b) H3O+, (c) NaBH4, MeOH

C.

(a) H2NHNTs (b) NaOEt, (c) ClCOOEt

D.

(a) H2NHNTs (b) 2 eq. nBuLi, (c) HCOH

OLi
O

Me3SiCH2OCH3

CH3

nBuLi

CH3

NaBH4

SiMe3
O

Ph3PCH2OCH3.HCl
nBuLi

H2O

CH3

MeOH
O

H2O

NaBH4

OH

MeOH
NH

NH T s

H2NHNTs

NaOEt

NH
N

nBuLi

COOEt

ClCOOEt

NH T s
N

Li

NaOEt
H2NHNTs

OH

nBuLi

Li
CH2 OH

HCOH

Study the following chemical conversion O

H3C

CHO
CHO

H3C

Suitable reagent

+
H3C

H3C

CH3

A. Michael addition followed by cyclisation

B. First aldol reaction followed by Michael addition

C. Two intramolecular aldol condensations
D. First Michael addition followed by intramolecular aldol condensation

Hammett plots provide useful information about several aspects of a reaction. Match
the following aspects reagarding reaction constant, and substituent constant, and
reaction given
L. Acid catalyzed hydrolysis of ethyl
benzoates ( = 0.03)

1. Reaction proceeds by SN1 pathway

M. Base catalyzed hydrolysis of ethyl

benzoates ( = 2.51)

2. Reaction accelerated by metamethoxy substituent and rate retarded by

para-methoxy substituent

N. Solvolysis of benzyl tosylates ( = -5.6) 3. Indication of two different RDS for

EDG and EWG
O. Reaction with different signs for for
EDG and EWG

4. Reaction largely unaffected by polar

effects of substituents

A.

L 1; M 2; N 3; O 4

B.

L 1; M 4; N 3; O 2

C.

L 4; M 2; N 1; O 3

D.

L 2; M 1; N 3; O 4

Substituent constant is a measure of the total polar effect exerted by substituent X

(relative to no substituent) on the reaction centre - Sign of the slope tells whether a reaction
rate is accelerated or suppressed by substituents.
Negative is indicates positive charge at the reaction centre in the transition state of the
rate-limiting step.
Positive is indicates negative charge at the reaction centre in the transition state of the
rate-limiting step.
The magnitude of is a measure of how susceptible a reaction is to the electronic
characteristics of the substituent.

Acetylenic protons are shielded due to -

A. Inductive effect

B. Hybridisation effect

C. Resonance effect

D. Diamagnetic
anisotropic effect

Study the following reaction AcO-

OBs

AcO-

OAc
OBs

1. The exo-norbornyl brosylate reacts 350 times faster than the endo-norbornyl brosylate

2. Both exo and endo brosylates produce exclusively exo-norbornyl acetate

3. Enantiomerically pure exo-norbornyl brosylate produces 100% racemic mixture

4. Enantiomerically pure endo-norbornyl brosylate produces slightly non-racemic mixture

(%ee < 10%)
Based on these observations, state which of the following steatment is correctly summarised the
above.
A. Exo-norbornyl brosylate undergoes the reaction with formation of non-classical carbonium
and endo-norbornyl brosylate reacts entirely by SN2 mechanism
B. Both exo and endo norbornyl brosylate entirely react by formation of classical carbonium.
C. Exo-norbornyl brosylate undergoes reaction entirely by SN1 and endo-norbornyl brosylate
reacts entirely by SN2 mechanism
D. Exo-norbornyl brosylate undergoes entirely via formation of non-classical carbonium and
endo-norbornyl brosylate reacts partially by SN2 mechanism and mostly via formation of
classical carbonium ion

OAc

OBs
H Exo -

Exo -

AcO-

NGP by H

Or through

CH

CH

Endo -

OBs

AcO-

OAc
CH

H
Non - classical carbocation

OBs

AcO-

AcO-

CH2

AcO-

AcO-

AcO-

CH
+

CH

AcO
Exo -

The C=C bonds, C-C and C-H bonds are act as neighboring group and forming
intermediates are called as non-classical or bridged carbonium ions.
AcO
6

AcOH

OBs

H
exo-isomer

AcO

non-classical ion

AcOH

OAc

Study the following reaction and identify the processes involved

A. 4 pi electron thermal con-rotatory electrocyclic reaction

B. 4 pi electron photochemical dis-rotatory electrocyclic reaction
C. (2 pi + 2 pi) photochemical cycloaddition reaction
D. (2 pi + 2 pi) thermal cycloaddition reaction

H
H

H
H

No.
of Process
electrons
involved

HOMO

Node

Transition
state

Symmetry

02

AntiAromatic

Plane
symmetry

No.
of Process
electrons
involved

HOMO

Node

Transition
state

Symmetry

01

AntiAromatic

Axis
symmetry

Photochemical

Thermal

Rotation allow

of Dis rotatory

Rotation allow

of Con rotatory

Identify the structures of mission X and Y components in the following Diels

Alder reaction

Ph
H3C

X + Y

H
H

CH3
Ph

A.

X =

and

Y=

Ph
H3C

B.

X =

and

Y=

CH3

Ph
C.

X =

and

Y=

Ph

CH3
D.

X =

and

Y=

The structures of X and Y components can be determined by using retro Diels

Alder reaction

Ph
H3C

H
H

H3C

Ph

Ph
H

H3C

The order of increasing reactivity towards nitration is -

A. Pyridine < quinoline < quinoline-N-oxide

B. Quinoline < Pyridine < quinoline-N-oxide

C. Quinoline-N-oxide < Pyridine < quinoline

D. Quinoline < Quinoline-N-oxide < Pyridine

Consider the nitration reaction on heterocyclic ring

It is the example of electrophilic substitution reaction, therefore rate depends on

electron density present in the ring

N
Reactivity towards nitration goes on increasing

N
O

In the synthesis of Ph-CO-CH2-CH2-CHO using diathiane following reagents

are used -

A. (i) NaOMe, (ii) H2C=CH-CO-Ph, (iii) H+, (iv) HgCl2/H+

B. (i) n-Buli, (ii) H2C=CH-CO-Ph, (iii) H+, (iv) HgCl2/H+

C. (i) NaOMe, (ii) Ph-HC=CH-CO-H, (iii) H+, (iv) HgCl2/H+

D. (i) n-BuLi, (ii) H2C=CH-CO-Ph, (iii) H+

When the dithiane is derived from an aldehyde such as acetaldehyde the acyl
proton can be abstracted by organolithium compounds or LDA in THF at low
temperatures.
HS

p-TSA

HS

H
formaldehyde

S
LDA

H S

Li

2+

R'-X
R'

1 D2O
2+

2 Hg / OH2

O
D

D- aldehyde

Li

R-CH3

1 R'COCl 1 R'COR''
2+
2+
2 Hg / OH2 2 Hg / OH2

R'
1

2+

2 Hg / OH2
O

R'

R'

O
1,2-diketone

Ni

O
R

R S
LDA

Hg / OH2
R'

R-X

1,3-dithiane

O
R

R'

OH
R''
a-hydroxy ketone

OH

B-hydroxy ketone

The structure of starting material A in the following photochemical Norrish

type reaction is O
h

CH3
A.

O
B.

CH3

CH3
O
O
C.

D.

The bond dissociation energy of a carbon-carbon bond adjacent to a carbonyl group

is small and photo-chemically undergoes hemolytic fission is called Norrish type-I
reaction or -cleavage.
The CO-C bond under goes fission forming alkyl and acyl radical. The acyl radical
under goes decarboxylation followed by recombination of two radicals or abstract
of hydrogen atom or secondary fission to get hydrocarbon and olefin.
A ketone having -hydrogen atom is under goes Norrish type-II reaction forming
an olefin and enol of a smaller ketone.

CH2
CH2

CO
n

CH2

.
CH
hv

CH2

.CO

-CO

CH2

(a)

.
CH

CH2

CH2=CH2 + CH3(CH2)n-3CH=CH2

CH2

CH2

(c)

(b)

CH2

CH2
CH3(CH2)n-1CH=CH2

Match the following photo-chemical reactions with their products

OAc

1. CH3CH2COCHMe2
H2C

a.

AcO
H3C

ONO

OH

2.
CH3

b.

OAc
c.

3.

(CH3CH2CO)*

OAc
4. MeCH2CH2COMe

A.

and (Me2CH)*

O
d. HON

CH3

1 a, 2 b, 3 c, 4 - d
B.

1 c, 2 d, 3 a, 4 - b
C.

1 c, 2 b, 3 d, 4 - a

D.

1 b, 2 c, 3 d, 4 - a

OAc

1. CH3CH2COCHMe2
H2C

a.

AcO
H3C

ONO

OH

2.

b.

CH3
OAc

(CH3CH2CO)*

c.

3.
OAc

and (Me2CH)*

4. MeCH2CH2COMe

d. HON

CH3

Barton reaction:Irradiation of organic nitrile introduced functionality on the unreactive aliphatic carbon atom carries atleast two hydrogen atoms.
R

H O N O

hv
-NO

organic nitrile

H O.

oxy-radical

Hshift

OH

alkyl radical

NO

NO

R
OH tautomer
ism
R

O OH

OH
N OH

OH2
HNO2

The Proton NMR spectrum of 2-bromo-2-methyl propane will show -

A.

Three quartets and a singlet

B.

Two doublets and a singlet

C.

Two singlets
D.

One singlet

Chemically equivalent and Magnetically equivalent protons

H3C

CH3

CH3
Br
2-bromo-2-methylpropane

The ratio of relative intensities of three molecular ion peaks of CH 2Br2 in the mass
spectrum is -

A.

M+ : (M + 2) : (M + 4) = 1 : 4 : 1
B.

M+ : (M + 2) : (M + 4) = 1 : 3 : 1
C.

M+ : (M + 2) : (M + 4) = 1 : 2 : 1
D.

M+ : (M + 2) : (M + 4) = 1 : 1 : 1

The intensity of isotope peaks are depends on natural abundance of the isotope.
The bromine has two isotopes, 79Br and 81Br with nearly equal abundance.
Cl 2

Cl

a = (M)

a
b

BrCl2

BrCl

Br

BrCl3

Br2Cl

b
a

Br3

Br2Cl2 b

b
d

Br3Cl3

e
Br3Cl2

Br2Cl3

b
a

a
d

Br3Cl

b
c

Br2

c = (M + 4)
d = (M + 6)
e = (M + 8)

b = (M + 2)

Cl 3

c
d

d
e

b
a

The major product formed in the following reaction is CH3

O

Me2CuLi

H3C

?
Et2O

I
CH3
A.

H3C

CH3
CH3
O

H3C
B.

CH3

CH3

C.

CH3
O

O
H3C

H3C

D.
CH3
H3C

CH3

CH3
O

H3C

CH 3

H3C

OLi

H 3C

H3C

Me2CuLi

CH 3
O

1,2 addition

Et 2O

I
CH3

Gilman Reagent (Reaction)

CH3

H3C

CH3
O

OLi

H3C

H3C
CH3

1,2 addition
CH3

OLi

H 3C

H3C

1,4 addition
CH3

CH3 H3C

CH3
OLi

H3C

CH3

O
H3C

1,4 addition
CH3

The major product formed in the following reaction is

O
Br

NaOMe

O
CH2

A.

COOMe
CH2
C.
O

B.

D.

The -halo ketones react with hydroxide or alkoxide ions produces carboxylic acid or
ester respectively. This reaction is called Favorskii rearrangement or oxidation
O

O
Br

NaOMe

HC

MeO

Br

ONa

CH 2

CH 2

NaOMe
NaOMe
NaOMe
O
CH2

Elimination reaction

HC

O
Br

Br

CH

COOMe
CH2

The major product formed in the following reaction sequence is -

1. DIBAL ( 1 equi.)
2. CH2=CHMgBr

O
3. PCC

O
H
O

CH2

C.

A.

CHO

H
O

O
B.

CH2

D.
O
H

CH3
H

CH2

Match the following

Compound

CMR chemical shift

a. Acetic acid

i.

95

b. Acetonitrile

ii.

115

c. Acetone

iii. 175

d. Carbon tetrachloride

iv. 205

A. a-iii, b-ii, c-iv, d-i

B. a-iii, b-iv, c-i, d-ii
C. A-i, b-ii, c-iv, d-iii
D. a-iii, b-i, c-ii, d-iv

Consider the following reaction, among a-c, correct statement are

O

OH
Et

Et
LiAlH4

a. The carbonyl group has enantiotopic faces

b. The hydride attack is re-facial
c. It is diastereoselective

A. a and c only
B. a and b only
C. b and c only
D. a, b and c

The major product formed in the following reaction sequence is (D)

1. m-CPBA
2. BF3 . Et2O

OH
OH
A.

B.
O
O

C.

D.

The major product formed during the following chemical reaction isNaH/THF

Br

H2C
CH2

CH2
H 2C

A.

B.

C.

D.

H 2C

NaH is the strong base and used for the aromatisation of ring after electrophilic
substitution of allyl group, it is fast step. First three products A, B, and C are formed by
the nucleophilic attack of benzene ring on allyl bromide and is slow step of reaction.
The intermediate carbocation formed is non-aromatic and having high energy. The
product D formed by the nucleophilic attack of carbanion of cyclopentadiene (formed
by the deprotonation by NaH) on allyl bromide. The carbanion (X) formed by the
deprotonation of CH2 group is more stable because of aromatisation of clopentadiene
as like indol system.
H

NaH/THF

H2C

CH2

Br

Carbanion stablized without disturbing the aromaticity

of benzene ring.
(Aromatic, More stable)

D.

The major product formed in the following concerned reaction is Heat

H
A.

H
B.

H
D.

C.
H

No. of electrons
involved

Process

HOMO

Node

Transition state

Rotation
allow

thermal

02

Aromatic

Dis
H

H
A

The major product formed during the following chemical reaction Br2/CH3OH

O
A.

C.

B.
O

Br

OCH3

OCH3

Br

Br

D.
O

OCH3

Br

Br

It is bromination reaction in presence of methanol. The intermediate

bromonium ion formed was stabilized by oxygen atom of pyran (internal
nucleophilic substitution). The formation of bromonium ion is the slow step. The
intermediate was react fastly with methanol rather than bromide anion.
Br
Br2/CH3OH

Br
O
(Bromonium ion)

HOCH3

Br

Br
or
O

OCH3

OCH3

Which of the following particles has the largest range in the given
medium if their initial energies are the same-

1. Alpha
2. Electron
3. Positron
4. Gamma

Or

Give an account on range of alpha, beta and gamma particles (nuclear

radiations).

Among the following which is synthetic equivalent of acyl anion -

1.
2.
3.
4.

-chloroacrylonitrile
Nitroethane and base
Ethylmagnesium bromide
Acetyl chloride & triethyl amine

The chemical species behaves opposite than expected is called as umpolung.

The nitro ethan treated with base forming carbaion which on hydrolysis in presence of
TiCl3/Pd-catalyst forming CH3CO- (acyl group) [Nef reaction].
Ethyl magnesiumbromide = ethyl anion; acetyl chloride/triethyl amine = acyl cation
and -chloroacrylonitrile is equivalent to anion of 2-oxo-proponic acid.

The major product formed in the following reaction is CH3

1. CF3COOOH
2. H3O+

H
CH3

CH3

OH

A.

CH3
OH

OH

OH
H

OH

OH

D.

C.

B.

CH3

OH
H

OH
H

Trifluoroperacetic acid is used for the epoxidation of olefines. The epoxide formed has
been protonated by using aqueous acid and then hydrolyzed. The attack of water takes
place on protonated epoxide from backside of the ring and forming cis-diol A.

Alkene
+
ketone

The structures of major products X and Y in the following transformation areO

+

Diene

Adduct
alkenone

Dienophil
e

1.

Formation of X is thermal [4+2]

cycloaddition reaction called Diels
Alder reaction. The substituent of
dienophile is endo rather than exo
when react with cyclic diene because
of maximum overlapping of orbitals
in T.S.
The formation of Y is photochemical
[2+2] cycloaddition of alkene and
carbonyl bond forming oxetane (four
membered cyclic ether) is called as
Peterno Buchi reaction (3).

hv

Y=

X=

2.

Y=

X=

X=

3.

Y=
O

4.

X=

Y=
O

O
HOMO

(endo form)
LUMO
HOMO

(exo form)
LUMO

The major product formed in the reaction given below is-

COOMe

H3C

CH3
COOMe

1.

2.
CH3
COOMe

3.

4.

CH3
COOMe

CH3
COOMe

According to the cis principle, the stereochemistry of the substituents in the diene and
dienophile is retained in adduct i.e. a dienophile with trans substituents will give an
adduct in which the trans configuration of the substituents is retained, while a cis
disubstituted dienophile will form adduct in which the substituents are cis to each others.

The major product formed in the following transformation is -

Grignard reagent in
presence of cuprous
salt

1-position

Conjugated
ketone
O

1. MeMgCl, CuCl
2.

4position

Cl

Ph

1.

4.

3.

2.
Ph

Allyl chloride

Ph

Ph

Ph

The ,-unsaturated carbonyl compound has two reaction sites as carbonyl carbon
(1,2-addition) and alkenyl carbon (1,4-addition) therefore Grignard reactant
forming two products. The reactivity of organo-Mg compound decreases by
adding cuprous salt forming new organo-copper compound of the type R2MgCu
or RCu which forming co-ordinate bond with carbonyl oxygen atom in six
membered transition state. Therefore Grignard reagent shows 1,4-addition in
presence of cuprous salt. The -substituted enol is then react with allylic chloride
before hydrolysis forming -allyl carbonyl compound (4).

The major product formed in the following transformation is COOH

1. N-bromosuccinimide

2. K O-tBu

Allylic carbon

COOH

1.
Strong
base

Allylic bromination
reagent

H
3.

COOH
2.
O

4.

N-Bromosuccinimide is good brominating agent at allylic position (-position) of

carbon-carbon double bond, C=O, benzene ring, etc. It is highly stereospecific
(react one functional group in presence of other) and stereoselective reagent. The
given organic compound contains C=C bond and COOH groups. The NBS
shows allylic bromination of C=C bond (because it shows free radical
mechanism & is stable in olefinic system) forming allyl bromide. If olefine has
two allylic position then bromination occurs at more substituted position because
of stabilization of free radical. In this example, bromination takes place at less
substituted position.
This compound is then treated with KO-tBu forming carboxylate anion which
shows intramolecular nucleophilic displacement of bromide ion through C=C
forming cyclic ester (3).

The major product formed in the following transformation is -

Organolithium compound in polar

tetramethylethylene diamine
O
1. sec. BuLi, TMEDA

2. MeI

Aromatic
amide

Organolithium compound
reacts with methyl iodide
O

O
N

1.

N
2.
O

O
3.

4.

Organo lithium compounds are very strong bases and nucleophiles. But they are
selectively used for ortho-substitution reaction. This amide group forming coordinate bond with lithiating reagent, therefore the ortho position is nearer to alkyl
group (nucleophile) and accept ortho-proton radialy forming orhto-lithiating amide
which on treatment with various electrophiles (Methyl iodide) forming orthosubstituted amide which is further hydrolyzed to carboxylic acid (2).

Among the following dienes, the one diene undergoes a degenerate Cope
rearrangement is H
1.

2.
H
H

3.

CH2
CH2
CH2

CH2
4.

The major product formed in the reaction of (S)-1,2,4-butanetriol with pentanone in the
presence of a catalytic amount of p-TSA is HO

HO
1.

Et

Et

2.

O
Et

Et

Et
OH

OH
3.

4.

Et

Et

O
Et

It is simple ketal formation reaction by using diol in presence of acid catalyst. The
given diol [(s)-1,2,4-butanetriol] is chiral molecule and after ketal formation (of 21,2,4-butanetriol
pentanone), its stereochemistry is retained (3).
CH2OH
HOCH2CH2

OH
H

CH2OH
HOCH2CH2

CH2OH

CH2OH
H

OH
CH2CH2OH
R

H
OH

HO

H
CH2CH2OH
S

Note: Lowest Priority groups on horizontal line [R-anticlockwise, S-Clockwise]

The major product formed in the following transformation is OH

t-BuOOH, Ti(O-iPr)4

(+) - diethyl tartrate

O

O
OH

1.

OH

OH

2.

O
OH
4.

3.
O

The asymmetric epoxidation of an allylic alcohol by using tert-butyl hydroperoxide in

presence of titanium (IV) iso-propoxide, and diethyl tartrate as catalyst is significant and
important method. This reaction is called as Sharpless epoxidation. The reaction gives
good yields and enantioselectivities (It is the organic synthesis which preserves or
introduce a desired chirality over broad range of substrate). During the reaction each
enantiomer of the tartrate ligand delivers the epoxide oxygen atom to one face of the
double bond, regardless the substitution pattern.
The oxygen atom is the delivered to the bottom face in the presence of L-(+)-diethyl
tartrate (the natural isomer) and to the top face in the presence of D-(-)-diethyl tartrate
(1).
[O] D-(-)-tartrate
[O] D-(-)-tartrate
slow
R2
R3

fast

R1 R
OH
H
fast
[O] L-(+)-tartrate

R2
R3

R1 H
OH
R
slow
[O] L-(+)-tartrate

The major product formed in the following transformation is CHO

NH2OH

P2O5

4.

3.

2.

1.

CN

CONH2

NHCHO

NC

Benzaldehyde reacts with hydroxyamine forming corrosponding oxime which is

further undergoes dehydration forming benzonitrile.
O

N
H

OH
H

H2N-OH
P2O5

O
H

P
O

The cope rearrangement involves

1. [1,5]-Sigmatropic rearrangement
2. [4+2] cycloaddition reaction
3. [3,3] sigmatropic rearrangement
4. 6-electrocyclisation reaction
The 1,5-dienes isomerizes {[3,3] rearrangement} on heating.
2'
1'

3'

[3,3] rearrangement

Which one of the following name reaction is example of atom economy reaction -

1. Wittig reaction
2. Grignard reaction
3. Dickmann condensation
4. Diels Alder reaction

Percentage Atomic Economy:

[Total number of atoms reacts /Total number of atoms present in product] x 100
Wittig Reaction: Aldehyde/Ketone + Wittig reagent gives alkene & phosphonium salt.
Grignard Reagent: Carbonyl compound + Grignard reagent gives alcohol & magnesium salt.
Dickmann Condensation: Ester gives cyclic keto ester and alcohol.

Diels Alder reaction: Diene + Dienophile gives cyclic alkene (4).

The major product formed in the following transformation is CH3

i. Ozonalysis

ii. NaOH
CH3
O

O
1.

2.

O
4.

3.
O

Ozonolysis reaction in important to determine the nature and position of double

bond. Alkene on ozonolysis forming aldehyde or ketone (by reductive
hydrolysis) and acid/ester (by oxidative hydrolysis). The cyclic alkene gives
dione/dial/oxoaldehyde.
The aldehyde or ketone formed undergoes intramolecular Aldol Condensation
forming cyclic Aldol which on dehydration give ,-unsaturated carbonyl
compound (1).
The stability of ring compound can be explain by angle strain, torsional strain,
etc.

The most suitable reagent to achieve the following transformation, given below is
OH

HO

HO

1. CrO3/H2SO4
2. MnO2
3. KMnO4/H+
4. RuCl3/NaIO4

CrO3/H2SO4 : Chromium trioxide in presence of acid catalyst is used for the oxidation
of secondary alcohol into ketone.
MnO2 : It oxidised allylic alcohol into conjugated carbonyl compound.
KMnO4/H+ : It is used for the conversion of diols to carbonyl compound/alkene to diol.
RuCl3/NaIO4 : It is used for the conversion diols to carbonyl compound.

The reagent suitable for converting oct-4-yne to trans-oct-4-ene is

1. H2/Pd-C
2. Pd-CaCO3/H2 (Lindlar catalyst)
3. NaBH4
4. Na/Liq.NH3

H2/Pd-C : Metal catalysed reduction, cis-addition of hydrogen, not controled to

alkene bond.
Pd-CaCO3/H2 (Lindlar catalyst) : Hydrogen shows cis-addition to alkyne bond
forming cis-isomer.
NaBH4 : It is not reduced alkyne group.
Na/Liq.NH3 : Metal in liquid ammonia (Birch reduction), metal donate electron forming
radical anion which is further react with second metal atom forming dianionic alkene in
which both negative charges are present on opposite of plane, which is furhter protonated
by ammonia forming trans alkene and sodamide.

Major product formed in the reaction below

N

OH
PCl5
Cl

MeO

MeO

Cl
1.

O
2.

N
H
Cl

3.

OMe

MeO
4.

N
H
Cl

N
H
O

Cl

N
H
OMe

It is example of Beckmann Rearrangement.

The Beckmann rearrangement (named after the German chemist Ernst Beckmann) is
an acid catalyzed rearrangement of an oxime to an amide. The cyclic oximes are
converted to lactones. The oxime forming intermediate with acid catalyst in which the
migration of the group (1,2-shift) from carbon to nitrogen is not depends on the migratory
aptitude value but depends on the orientation of the group. The group which is anti to
the hydroxyl group of oxime is only migrates towards nitrogen. Therefore, it is highly
stereospecific reaction. (2)

The reaction of phenyl acetylene with one equivalent of methyl magnesium bromide
followed by reaction with banzaldehyde providesOH
Ph

OH
1.

3.

2.

Ph
Ph

H3C

CH3
Ph

H
4.

Ph

Ph

Ph

CH3

HO

Grignard Reagent is strong nucleophile and base. The acetylenic proton is acidic in nature.
It undergoes deprotonation forming new phenylacetylenyl Magnesium bromide (New
Grignard reagent) which is then react with benzaldehyde forming corresponding alcohol.

The most suitable reagent to achieve the following transformation, given below is (3)O

Clemmensen
Reduction
MeO

MeO

1. NaBH4
2. B2H6
3. Zn-Hg/HCl
4. NH2-NH2/HCl

Acetophenone can be converted to phenol by reaction with (1) -

Baeyer
Villiger
Oxidation

1. m-CPBA followed by the base catalyzed hydrolysis.

2. Conc. HNO3
3. Iodine in NaOH
4. Singlet oxygen followed by base catalyzed hydrolysis.

The major product formed in the following transformation is (2) O

Cl

H2N-NH2

Woulf
Krishner
Reduction

KOH
Cl
1.

COOH

NHNH2
2.

3.

4.

The following transformation is carried out by using (4)O

1. BH3:THF followed by H2O2/NaOH

2. Alkaline KMnO4/NaIO4 (oxidation)
3. Pyridinium chlorochromate
4. PdCl2/CuCl2/O2/H2O

Wacker
Process

Reductive Ozonolysis of which of the following compounds will give (X) and YO

HCHO
(Y)
OHC
(X)

(A)

(B)

(C)

(D)

Ozonolysis is used to determine the nature double bond (mono, di, tri and tetra
substituted alkene) and its position in skeleton (terminal, in ring, etc). The
ozonide intermediate formed on reductive cleavage gives aldehyde and ketones.

Reaction of m-cresol with chloroform and alkali (Reimer-Tiemer reaction) will

give the following compound as the major product.
OH
CHO
H3C

OH

OHC

(b)

(a)

OH

OH

(c)
H3C

(d)
H3C

Reimer-Tiemann
reaction
phenol,
anisole (aryl ether), and certain aromatic
heterocyclic compounds are formylated
by using chloroform (or carbon
tetrachloride) and hydroxide anion. The
incoming group is directed at orthoposition of OH/-OR group, if both the
ortho-positions are blocked then
incoming group attacks at para-position.
During this reaction, o-substituted
product is dominant but if one of the
ortho-position is blocked, then
incoming group goes to the paraposition.

H3C

CHO

CHO

:CCl

OH + CHCl3

:CCl

:CCl
OH

OH

+ Cl

: CCl

(Dichlorocarbene)

..CCl

..CCl

CHCl2

H
2 KOH

OH
CHO

OH2
Acid

CHO

CH(OH)2

Steroidal 2-alkene (A) gives two different products with I2/AgOAc, H3O+ and OsO4H2O reagentsI2/AgOAc, H3O

HO

HO

HO

OsO4, H2O

HO

RCOOAg

+
silver salt of carboxylic acid

I2

RCOOI

R
O
RCOOI

+
(olefin)

+
I
iodonium ion

AgI

R
+
NGP of RCOO-

OCOR

group

RCOO

Ag-OOCR

+
H3O

HO

OH
+
OH

HO
(trans-diol)

Osmium tetraoxide is used

for the synthesis of vicinal
diols from alkenes.

Pyridine

O
O
O

Os
O

Os
O

Prevost reagent is used for

the oxidation of olefin into
trans diol. Prevost reagent
is a mixture of silver salt of
an acid such as the benzoic
acid or acetic acid and
iodine.

NaHSO3
OH2

+ H2OsO4
HO

OH

OsO3 + H2O

COOH
1.
N

H3O+

(C4 H9)3SnH

Benzene

OsO4

Wilkinsons catalyst

ZnCl2

+
O
NHNH2

Fischer Indol
synthesis

CH3
a.

3.

4.

Br2, NaOH

ii. NH3

O
I

2.

i. SOCl2

Beckmann
rearrangement

Scrap Quinoline
synthesis
H3C
b.

Glycerol, H2SO4

NH2

PhNO2, FeSO4