GRIGNARD REAGENT, REDUCTION & ALKANES

Introduction of Organometallic compounds

Organometallic compounds are the organic compounds in which a metal atom is directly attached to carbon
atom through covalent bond or ionic bond. For example
C–M or e.g. R-MgX, R2CuLi, R2Zn

(Where C is a carbon atom of an organic molecule and M is a metal atom)

If the metal atom is attached to oxygen, nitrogen. sulphur, etc., then such an organic compound is not
regarded as an organometallic compound. The following structural formula do not belong to the family of
organometallic compounds.

RONa (Sodium alkoxide). CH3COONa (Sodium acetate), CH3COOAg (Silver acetate), RSK (Potassium
mercaptide) RNHK (N-Alkylpotassamide), (CH3COO)4Pb (Lead tetraacetate), etc.

Note : It should be noted that (CH3)4Si (Tetramethylsilane, TMS) is also not an organometallic compound
because silicon is a nonmetal.
Most important examples of organometallic compounds are Grignard's reagents. In Grignard's reagent, the
carbon and magnesium atoms are bonded with each other through polar covalent bond and magnesium atom
is attached to halogen by ionic bond.

(Functional part of a Grignard's reagent molecule)

In organometallic compounds, the metal atom can be bonded to carbon atom of a hydrocarbon radical
(Saturated, unsaturated, aliphatic, alicyclic or aromatic) or carbon atom of a heterocyclic radical. Some
examples are given below.
1. Saturated Aliphatic Grignard's reagent
R – MgX (Alkylmagnesium halide)
CH3 – MgI (Methylmagnesium iodide)

2. Unsaturated Aliphatic Grignard's reagent

(i) Alkenyl Grignard's reagent
CH2 = CH – CH2 – MgX (Allylmagnesium halide)
(ii) Alkynyl Grignard's reagent
CH  C – CH2 – MgX (Propargylmagnesium halide)

3. Alicyclic Grignard's reagent

(Cyclohexylmagnesium halide)

4. Aromatic Grignard's reagent

(Phenylmagnesium halide)
C6H5CH2MgCl (Benzylmagnesium halide)

Preparation
Dry and pure
RX + Mg  Ether
  RMgX
Ether is used as a solvent because it is a Lewis base that donates its lone pair of electrons to electron-
deficient magnesium atom, therefore providing stability to the Grignard's reagent by completing the octet on
magnesium atom.



Process : To an etherial solution of alkyl halide Mg metal is added at very low temp. (0 – 5°C). A vigorous
reaction takes place , and a solution of G.R. is obtained. It cannot be evaporated to get it in solid state. The
reaction will be explosive. It is stable only in solution state.
Reactivity order with respect to X (For preparation of RMgX)
R–X:

Iodides forms organometallic compounds at the fastest rate.

Structural stability of G.R.
If the alkyl part has more stable negative charge, then RMgX is more stable. It will be less reactive
e.g. CH3 – CH2 – MgX ; CH2 = CH – MgX ; CH3C  C – MgX
Reactivity order : 1>2>3
Stability order : 1<2<3

Reactivity order of Grignard's reagent

On having same hydrocarbon radical, the order of reactivity of Grignard's reagents will be as follows :
RMgI > RMgBr > RMgCl

Reactivity order with respect to active H

Acidic H > – CHO > > > >R–X

Except X (halogen) all other functional groups must be absent in the alkyl group otherwise. G.R. will be
destroyed by internal reactions.
[– NO2, – CN must also be absent]

Reduction
Catalytic Hydrogenation :
Catalyst
| |
General Reaction C = C + H2 –C–C–
| |
H H
(syn addition)
Hydrogenation of an alkene is an exothermic reaction (Hº  – 120 kJ mol–1)
Ni
R  CH  CH  R  H2   R  CH2  CH2  R  heat
Partial Reduction
(a) Lindlar's catalyst :
It is a poisoned palladium catalyst (composed of powdered barium sulphate coated with palladium) poisoned
with quinoline or sulphur. Nickel boride Ni2B(P-2 catalyst) (made from sodium acetate and sodium borohidride)
is an excellent alternative catalyst for the conversion of alkyne into alkene. (syn addition)
The partial reduction of alkyne to alkene is heterogeneous hydrogenation with Lindlar's catalyst.
C2H5 CH3
H2 Lindlar's catalyst
CH3 – CH2 – C  C – CH3 C=C (syn addition)
or Ni2B
H H
Acid chloride reduced to aldehyde by using Pd/BaSO4 catalyst is called Rosenmund Reduction.
O
|| H /Pd-BaSO
(i) CH3 – C – Cl
2 4
CH3 – CHO
H2/Pd
(ii) O2N – CH = CH – CH2 – CH3 H2N – CH2 – CH2 – CH2 – CH3

H2/Pd or Pt
(iii) CH = CH2 CH2 – CH3

(b) Reduction by Dissolving Metals :

The general mechanism of reduction by dissolving metals is based on the fact that the metal acts as a
source of electrons first an electron adds to the substrate causing fission of a single bond into a free radical
and an anion or it can adds to a double bond forming a resonance-stabilized radical ion.
e
A– B A + B: or A: + B
e
A= B : A – B or A + B:
Reduction by Na or Li/NH3 (Birch reduction) :

Mechanism :
Reagents Na(or Li, K) + liq NH3  Na+ + e– (solvated electron)

R R H
Na H – NH2
R–CC–R C=C C=C
R R

Na

R H R H
H2N – H
NaNH2 + C=C 
C=C (anti addition)
Na
H R R
(~ 100%)
(trans alkene)
Typical example of reduction for aromatic system :
(electron releasing group – R, – OR, – NH2)
G G

H
Na/NH3
H H
H
(electron withdrawing group – NO2, COOH, – CHO, – CN)
G
G H

Na/NH3

H H

Reduction by Na/C2H5OH [Bouvealt-Blanc reduction]

Na/C2H5OH
(a) CH3CHO CH3CH2OH
Acetaldehyde Ethanol

Na/C2H5OH H3C
(b) CH3–COCH3 CHOH
H3C
Acetone propane-2-ol

O
|| Na/C2H5OH
(c) CH3 – C – OC2H5 CH3CH2OH
H3O+

Ethyl acetate Ethanol

Reduction by metal hydrides and alkoxides :

LiAlH4(LAH) Lithium aluminium hydride (strong reducing agent) :
NaBH4 Sodium borohydride (Mild reducing agent) :

Mechanism :
 O
|| R2C=O
H3Al – H C H3Al – O – CHR2 H2Al (OCHR2)2
R R
R2C = O

H3O R2C=O
4 R2CHOH Al– (OCHR2)4 HAI (OCHR2)3

DIBAL-H (Diisolbutyl Aluminium Hydride) (ALANE)

Most important alane is diisobutyl aluminium hydride. It runs parallel to LAH (Lithium aluminium hydride) as
a reducing agent but it is more selective.

LiAlH4 – THF
(a) Ph – CH = CH – COOC2H5 Ph – CH2 – CH2 – CH2OH + C2H5OH
H2O

DlBAL-H

Ph – CH = CH – CH2OH + C2H5OH
By DIBAL at ordinary temperature esters are reduced to alcohols but at low temperature esters are reduced
to aldehyde.

O
||
DIBAL
(b) C6H5 – C – OCH3 C6H5CH2OH
toluene 25ºC

DIBAL toluene – 78ºC

C6H5CHO
LAH reduce RCN to amine but DIBAL is found to be reduce it to aldehyde.

LiAlH4 – THF
(c) CH3 – C  N CH3 – CH2 – NH2
DIBAL
25ºC

CH3 – CHO

MPV Reduction (by isopropyl alcohol and aluminium isopropoxide)

Al(OCHMe2)3
R – C – R' + CH3 – CH – CH3 R – CH – R' + CH3 – C – CH3
|| | | ||
O OH OH O

Stephen's Reduction :
When reduction of compounds is carried out with acidified stannous chloride (SnCl2/HCl) at room temperature,
imine hydrochloride is obtained which on subsequent hydrolysis with boiling water gives aldehyde. This
specific type of reduction of nitrile is called stephen's reduction.

LiAlH4 or Na/C2H5OH
R – CH2NH2
(Complete Reduction)
(1º Amine)
R–CN
(i) SnCl2/HCl (ii) H2O
R – CHO
(Partial Reduction) Aldehyde

Clemmensen's Reduction
Used to get alkane from carbonyl compounds :
 Zn – Hg/HCl
C=O CH2
2 3
sp sp

Clemmensen reduction is not used for compounds which have acid sensitive group.

Wolff-kishner reduction (NH2NH2/KOH) :

Used to get alkane from carbonyl compounds
NH2 – NH2/KOH
C=O CH2
Using high boiling
2 solvent (ethylene glycol) 3
sp sp
Wolff-kishner reduction is not used for compounds which have base sensitive groups.

By Red P & HI :
All the functional groups reduced into corresponding hydrocarbon.
Red P + HI
(a) R – C – OH R – CH3
|| 
O
Red P + HI
(b) R – C – Cl R – CH3
|| 
O
Red P + HI
(c) R – C –OEt R – CH3
|| 
O
Red P + HI
(d) R–C–R R – CH2 – R
|| 
O
Red P + HI
(e) CH3 – C – OH CH3CH3
|| 
O
Red P + HI
(f) CH3 – C – CH3 CH3CH2CH3
|| 
O

Various functional groups and their products by the use of different reducing agents
 t
S. No. Group Product H2 + Catalyst LiAlH4 in ether NaBH4 in EtOH LiAlH(OBu )3
in THF

1 – CHO – CH2OH + + + +

2 C=O CHOH + + + +

3 – CO2H – CH2OH – + – –

4 – COOR' – CH2OH – + – –

5 – CONH2 – CH2NH2 – + – –

6 – COCl RCH2OH + + + +

7 – epoxide alcohol + + – –

8 – CN – CH2NH2 + + – –

RNO2 RNH2 + + – –
9

10 C=C CH – CH + – – –

(*) double bond can be reduced by LiAlH4/THF only in cinnamic system.

LiAlH4 – THF
For eg. Ph – CH = CH – CHO Ph – CH2 – CH2 – CH2OH
H2O

ALKANE
INTRODUCTION :
* Saturated hydrocarbons are known as alkanes or paraffins (Less reactive).
* Alkanes with carbon chains that are unbranched are called normal alkanes. Each member of the series differ
from the next higher and next lower member by >CH2 group.
* General formula : CnH2n+2
3
* All the carbon atoms in alkanes are in sp state of hybridization and geometry is tetrahedral.
* All the bond angles are tetrahedral angles i.e., H–C–H or H–C–C bond angle is 109º28'

 Properties
3
C–C
3 3
C–H
(i) Overlapping sp – sp sp – s
(ii) Bond length 1.54 Aº 1.112 Aº
(iii) Bond energy 80 – 85 kcal 98.6 kcal

METHODS OF PREPARATION :
(i) From Carboxylic acids :
(a) By de-carboxylation :

RCOONa + NaOH/CaO  R–H + Na2CO3
Sodium carboxylate Soda lime Alkane
 (n) (n – 1)

[b] Kolbe's electrolytic synthesis :

Electrolys is
2RCOONa + 2H2O     R – R + 2CO2 + H2 + 2NaOH
* Methane cannot be prepared by this method.
2CH3COONa + 2H2O  CH3–CH3 + 2CO2 + 2NaOH + H2

Anode Cathode
Mechanism :
Ionic free radical :
– +
2CH3COONa 2CH3COO + 2Na
At anode :
–  –
2CH3COO 2CH3COO + 2e
2CH3COO




2CH3 + 2CO2 A
CH3 + CH3 C2H6
At cathode :
+ –
2Na + 2e 2Na
2Na + 2H2O 2NaOH + H2 A
(ii) Reduction of Alkyl Halides :
Re duc tan t
R–X   R–H + HX
Alkyl halide Alkane
Reductants : Zn–Cu couple/EtOH, Na–EtOH, Zn–HCl, Pt or Pd or Ni/H2 Al–Hg/EtOH, LiAlH4 etc.

(iii) Wurtz Reaction :


R–Br + 2Na + Br–R   
Dry Ether R–R + 2NaBr
Alkane
* Methane cannot be prepared by this method.
* The alkane produced is higher and symmetrical i.e., it contains double in the number of carbon atoms
present in the alkyl halide taken.
* When the two reacting alkyl halides are different, a mixture of three different alkanes is obtained. So the
Wurtz reaction is not useful for preparing alkanes containing odd no. of C atoms.
C2H5I + CH3I  C2H6 + C3H8 + C4H10
* Mechanism : Wurtz reaction may proceed via the formation of organometallic compound or alkyl free radicals.
[i.e. Both ionic and free radical mechanisms are proposed]
Dry ether
2C2H5Br + 2Na    C2H5–C2H5 + 2NaBr

(A) Ionic Reaction Mechanism :

+
C2H5Br + 2Na  C2 H5– Na + NaBr
Ethyl sodium
(organo metallic)
+
C2 H5– Na + C2H5Br  C2H5–C2H5 + NaBr
n-Butane
(B) Free radical Reaction Mechanism :

C2H5Br + Na  C2H5 + NaBr
Ethyl free
radical
  Dimerisation
C2H5 + C2H5     C2H5–C2H5
(iv) From Grignard reagent :
Z H
RMgX   RH + Mg(Z)X
Z–H [compound containing active hydrogen]
HOH, NH3, RCCH, C6H5OH, CH3COOH, RNH2, R2NH, Pyrrole, C2H5OH etc.
(v) From Alkenes and Alkynes (Hydrogenation) :
Ni / 200 º
R–CH=CH–R' + H2   R–CH2–CH2 R'
Olefin Alkane
 Ni / 300 º
R–CC–R' + 2H2   R–CH2–CH2–R'
* When the catalyst are Pt or Pd, hydrogenation proceeds smoothly at ordinary temperature and pressure.
* With Nickel catalyst, higher temperature (200º – 300ºC) and pressure are needed. (In this case the reaction is
known as Sabatier Senderen's reaction)
* With Raney Nickel, the reaction takes place at room temperature.
Ni / Al + NaOH  Ni in powdered form (Raney Nickel)
In this reaction following alkanes are not formed from unsaturated hydrocarbons
Alkene / Alkyne  Methane
Alkene / Alkyne  Neopantane
Alkyne  Isobutane
* The reaction is exothermic. The heat released in the reaction is known as heat of hydrogenation.
o
(vi) Reduction of Alcohols, Aldehydes, Ketones and Acids by Red P and HI (150 C) :
(a) By the reduction of alcohols :
Re d P
R–OH + HI   RI + H O
150 ºC 2


R–I + HI  R–H + I2
*Since iodine is produced during the reaction, it may react with the resulting alkane, so it is removed by
adding red phosphorus.
2P + 3I2  2PI3 (volatile)
(b) By reduction of acid :
Re d P
RCOOH + 6HI   RCH + 3I + 2H O
150 ºC 3 2 2
(viii) From dialkyl zinc :
R' X
R2Zn   R–R' + RZnX
(ix) Corey-House Synthesis :
Ether
R–Br + 2Li  R–Li + LiBr
Alkyl bromide Alkyl lithium
Ether
2R–Li + CuI   LiR2Cu + LiI
Lithium dialkyl
cuprate
R2LiCu + R'–X  R–R' + RCu + LiX
Alkane
* This method is useful for prparation of alkanes containing odd no,. of c-atoms.
Specific methods of preparation of CH4 :
12H O
(i) Al4C3  2 3CH4 + 4Al(OH)3
4H2 O
Be2C    CH4 + 2Be(OH)2
Heat
(ii) CS2 + H2S  CH4
Cu
(iii) Sabatier Senderen's :
Ni, 
CO2 + 4H2  CH4 + 2H2O
Ni, 
CO + 3H2  CH4 + H2O

PHYSICAL PROPERTIES :
(i) Alkanes from C1–C4 are gases.
C5–C17 are liquids, C18 – onwards are waxy, white solids.
Note :Neopentane is a gas.
(ii) Boiling point :
1
 Boiling point  molecular weight (for homologes) 
Branches
(for isomers)
e.g. order of boiling point
n-pentane > isopentane > neopentane

(iii) Melting point : Alkanes containing even no. of carbon atoms have higher melting points than it's next
higher or next lower homologue having odd no. of carbon atoms.It is because of more symmetricity of alkane
 molecules with even no. of carbon atoms as compared to alkanes with odd no. of carbon atoms.

C C C C C C

C C C C C C C
(Both methyl groups are directed in opposite direction) (Both methyl groups are on the same side)

* Alkanes are colourless, odourless and tasteless.

* Alkanes are lighter than water. These are insoluble in water and soluble in organic solvents.

CHEMICAL REACTIONS
1. Stability
2. Substitution reactions :–
(a) Halogenation (b) Nitration
(c) Sulphonation (d) Chlorosulphonation (Reed reaction)
3. Oxidation :
4. Cracking / Pyrolysis :
5. Isomerisation
6. Aromatization
7. Addition of CH2

1. Stability
Although alkanes are chemically unreactive under ordinary conditions due to the presence of strong C–C and
C–H sigma () bonds, yet they give following reactions under special conditions
.
2. Substitution Reaction
(a) Halogenation :
h
R–H + X2  R–X + HX
* Reactivity order of hydrogen atoms in alkanes is
3ºH > 2ºH > 1ºH
*Reactivity order of halogens is
F2 > > Cl2 > Br2 > I2
Fluorine can react in drak. Cl2 and Br2 require light energy. I2 does not show any reaction at room temperature,
on heating it shows iodination.
 Fluorination –
*Direct-fluorination of alkanes is usually explosive.
CH4 + F2  Carbon black (explosive reaction)
*It is carried out successfully by diluting fluorine with nitrogen (Inert gas).
CH4 + F2  CH3F + HF
 Chlorination –
2 Cl 2 2 Cl Cl
CH4 + Cl2  CH3Cl 
  CH2Cl2 
  CHCl3 
  CCl4

 The monochloro derivative of alkane is obtained as a major product by taking alkane in excess.
h
e.g. CH4 + Cl2   CH3Cl + HCl
Methane Methyl chloride
(excess)
* When chlorine is in excess, carbon tetrachloride will be the major product.
h
e.g. CH4 + Cl2   CCl4
Methane (excess) (Main)
Chlorination of alkanes takes place in the following conditions.
* No reaction at room temperature in darkness.
* At 300ºC in darkness.
* At 100ºC in the presence of organic peroxides.
* At 150ºC in the presence of Tetra ethyl lead

 Chlorination of methane is based on free radical mechanism and it completes in the following three steps :
(a) Chain initiating (first) step
 h  
Cl2 
 Cl Cl
(b) Chain propagating (second) step
 
Cl + CH4 CH3 + HCl
 
CH3 + Cl2 CH3Cl + Cl
(c) Chain terminating (third) step
 
CH3 + Cl H3Cl
 
CH3 + CH3 CH3 – CH3
 
Cl + Cl Cl2

 Bromination : Bromination of alkanes is similar to chlorination but not so vigrous.

 Iodination : Iodination of alkanes is slow and reversible.

CH4 + I2 CH3 – I + HI
* Iodination may be carried out in the presence of an oxidising agent such as HIO3, HNO3, HgO, etc. which
destroys the HI as it is formed and so drives the reaction to the right.
5HI + HIO3  3I2 + 3H2O

(b) Nitration : When a mixture of vapour of alkane nitric acid is heated at high temperature (400°C – 450°C)
a mixture of all possible nitroalkanes is obtained (The reaction involves both C–C and C–H bond cleavage).
high temp .
R – H  HO – NO 2    R– NO2 + H2O
(c) Sulphonation : In this reaction, hydrogen atom of the C–H bond is replaced by –SO3H group.

R – H  HO – SO3H   R–SO3H + H2O
(Fuming) Alkane sulphonic acid
* Fuming H2SO4 = mixture of SO3 + Conc. H2SO4 = H2S2O7 (Oleum)

* Alkanes containing 6or more carbon atom and lower branched alkens (not lower unbranced) can be
sulphonated).

Oxidation
(a) Complete oxidation or combustion : All alkanes readily burn in excess of air or oxygen to form CO2
and H2O.
 3n  1 
CnH2n+2 +   O  nCO + (n + 1) H O + heat
 2  2 2 2

Volume of alkane 2
 Volume of oxygen =
3n  1
(b) Catalytic oxidation :
1 Cu
(i) CH4 + O  CH3OH
2 2 250º C / 100 atm.
MoO
(ii) CH4 + O2  HCHO
270º C / 100 atm.
O
||
( CH3COO)2 Mn,
(iii) R–CH3        R – C – OH
(5) Isomerisation : Straight chain alkanes are converted into their branched chain isomers when heated in the
presence of AlCl3 + HCl at 300ºC.
CH3
AlCl3 HCl
|
e.g. CH3–CH2–CH2–CH3    CH3 – CH – CH3
300 º C
*If we take n-heptane then it converts into highly branched alkane (triptane).
 CH3
|
e.g. CH3–(CH2)5–CH3  CH3 – C – – CH – CH3
| |
CH3 CH3
n-heptane Triptane [2,2,3–Trimethyl butane]
*If we take n-octane then it converts into most stable form iso-octane.
CH3
|
CH3–(CH2)6–CH3 CH3  C  CH2 – CH – CH3
| |
CH3 CH3
n-Octane iso-octane [2,2,4–Trimethyl pentane]
*Isomerisation of alkanes is of great importance in petroleum industry to increase the octane number of
petrol (gasoline).
(6) Aromatization, hydroforming or catalytic reforming : The conversion of aliphatic compounds into aromatic
compound is referred to as aromatization. Alkanes having six or more carbon atoms are heated at 600ºC in
the presence of a catalyst such as Cr2O3 supported over alumina or Pt, an aromatic hydrocarbon results.

CH 3
CH 2 CH3 Cr2O3 / Al2O3 or
| | Pt (catalyst)


e.g. (i) CH2 CH2 600ºC

CH2
n-Hexane
Cr2O3 / Al2O3 or
Pt (catalyst)
(ii) CH3(CH2)5 CH3 

600ºC

n-Heptane Toluene
* Aromatization involves cyclization and dehydrogenation.
Dehydrogenation :
Cr O / Al O
CH3–CH2–CH3   2   CH –CH=CH + H
2 3 3
e.g. 600 º C 3 2 2
Propane Propene
Special properties of CH4

(i) CH4 + O3  HCHO + O2 + H2O
(ii) CH4 + H2O  CO + 3H2
Synthetic gas
1500 º C
(iii) 3CH4 + O2    C2H2 + 5H2 + CO2
acetylene
Electric arch
(iv) CH4 + N2    HCN + H2
Al O
(v) CH4 + NH3 2 
3
 HCN + H2
High temp.
Important points :
*Methan is also called marsh gas or damp fire.
*CNG (Compressed naturel gas)  CH4 + propane + butane + Higher alkane. 84%
*LPG is called as liquified petroleum gas or kitchen gas or domestic gas.(Mixture of liquid propane + liquid
butane and other liquid paraffines)
*The mixture of n-butane and isobutane called calor gas.
Single Choice Questions :
1. Which of the following compound give benzene on reaction with PhMgBr

1. 2. 3. 4. CH3–CCH

5. 6. CH3NH2 7. HCN 8.

9. CH3SH 10.

(A) 2,3,4,5 (B) 7,8,9 (C) 2,4,5,7,10 (D) All

2. The compound 'Y' can be prepared by using the reagents.

+ CH3MgBr

(A) II only (B) I, II (C) II, III (D) All (I, II, III, IV)

3. 2-Phenylcycloprop-2-en-1-one is allowed to react with phenylmagnesium bromide and the reaction mixture
is hydrolysed with perchloric acid. The product formed is :

Ph
|
(A) Ph  C  C  CHO (B) (C) (D)
|| |
O OH
4. In which of reaction alcohol will form

(A) (B) PhMgBr + H – C  N 

(C) PhMgBr + CH3 – C  N  (D) PhMgBr + H – C  CH 

 3 H O
5. CH = CH2 
 Major products is. Product (A) is

(A) (B) (C) (D) None of these

6. What is the major organic product of the following sequence of reactions ?

(A) (B) (CH3)2CHCH2CH2OH

(C) (D) (CH3)2CHCH2CH2CH2OH

7. Which of the following compound reduced by NaBH4 ?

(A) (B) CH3 – NO2 (C) (D)

(i) LiAlH4
8. 
(ii) H2 O

 Relationship between products is

(A) Meso (B) Racemic mixture (C) Diastereomer (D) None

(i) LiAlH4
9. 
(ii) H2 O

 (A) Product (A) is

(A) Meso (B) Diasteromer (C) Racemic mixture (D) None

(1) PhMgBr
10.   A
(2) H

The product of the above reaction is

(A) Racemic mixture (B) Diastereomers
(C) Structural isomers (D) (trans) 3-phenyl but-2-en-2-ol
(1) PhMgBr
11. CH3– C  N 
(2) H3O
A

Product A is

(A) (B) (C) (D)

12.

The final product is

 (A) (B)

(C) (D)

13.

The products A and B respectively are

(A) , (B) ,

(C) , (D) ,

14. CH Mg Br CH Mg Br CH Mg Br
H2 O
 
3

  
3

  
3

  Product

(A) + (B) +

(C) (D) +

15.

Products A and B respectively are

 (A) , (B) ,

(C) , (D) ,

16.

The products A and B respectively are

(A) , (B) ,

(C) , (D) ,

17. R–CN

(1) (2) (3) (4)

When the compounds 1, 2, 3 and 4 reacted with a specific reagent ‘K’, the product obtained was RCHO. The
reagent K is/are
(A) H2/Pt (B) LiAlH4 (C) DIBAL (D) None of the above
18. 2, 4 DNP in used in the test of
(A) Carboxyl (B) Carbonyl (C) Ether (D) Alcohol

19.

Identify the functional group of one of the intermediates formed in wolff Kishner reduction
(A) Oxime (B) Hydrozone (C) Schiff’s base (D) Enamine
LiAlH4
20. CH3 – C  N  A
LiAlH4
 B
The relation between A and B
(A) Functional Isomers (B) Homologous
(C) Positional Isomers (D) None of the above
21. Identify the functional group

(A) Enamine (B) Hydrozide (C) Hydrozone (D) Imine

22.

Product P is

(A) (B) (C) (D)

23.

The products A and B are respectively

(A) , CH3–COOH (B) CH3 – COOH, CH4

(C) , (D) ,

24.

(A) (B) (C) (D)

25. Major product is :

(A) (B) (C) (D)

26. x

x = number of -ketoacids which could undergo the above reaction (include stereo isomerism). The value of
x is
(A) 1 (B) 2 (C) 3 (D) 4
27.* Which of the following reaction is/are correct

OH
(i) Mg / THF
(A) Br  CH2  CH2  CH2  C  CH3 (  
ii) H2O
||
O CH 3

O O
Cl || ||
H–C–O C
(B) Mg
THF


O
||
Mg / Ether Cl – C – Cl
(C) Br – (CH2)4 – Br     O

Me Me Ph Me Me
(i) Ether Et H Et H
(D) Et H + C + HO Ph
|| (ii) H2O Ph OH
MgBr Me
O
Me

28. PhMgBr + CO2 

H
 Major product is :

(A) (B) (C) (D) No reaction

29. CH3 – C  N 

H O
Major product is :
3

(A) CH3 – CH2 – NH2 (B) (C) (D) CH3 – CH = N – OH

30.  Major product is :

H O
3

(A) CH3OH, CH3NH2 (B) CH3–NH2, HCOOH

(C) CH3 – NH – CH3 (D) CH3 – N = C = O

31. PhMgBr +  Major products is :

(A) Phenol (B) Benzyl alcohol (C) 2-Phenyl ethanol (D) 1-Phenyl Ethanol
32. CH3MgBr + HOCl  Major product is :
(A) CH3 – OH (B) CH3 – Cl (C) CH3 – OCl (D) CH4

33. CH3MgBr +  A
The product

(A) (B) (C) CH4 (D) No reaction

Paragraph for Questions Nos. 34 to 35
Carbonyl group show characteristic reaction of nucleophilic addition in which nucleophile attack is rate
determing step on carbonyl carbon.
34. Which pH is suitable for ozime formation
(A) 4 – 5 (B) 1 – 2 (C) 8 – 10 (D) 12 – 14
35. Which of the reactant show geometrical isomerism when it react with hydrazine (NH2 – NH2)

(A) (B) (C) (D)

MCQ
36. In which of the following reactions product will be aldehyde ?
(i) O (1) HBr / R2 O2
(A)  3
(ii)H O
 (B) CH3 – CH = CH2 
(2) aq.KOH(3)PCC


2

B H HOH / HgSO 4 / H2SO4

(C) CH3 – C  CH 
2 6
NaOH,H2 O2 (D) CH3 – C  CH 
(Kucherov reaction)



37. Stability of hydrates of carbonylc compounds depends on ;

(A) Steric hindrance (B) Presence of –I group on gemdiol carbon
(C) Intramolecular hydrogen bonding (D) angle strain in carbonyl compound
38. In which of the following reaction diastreomer will form ?

(A) LiAlH4 (B) LiAlH4

   

(C) LiAlH4 (D) LiAlH4

   

39. 3-methyl-3-hexanol can be prepared by

((A) CH3 Mgl and 3-hexanone, followed by hydrolysis
(B) C2H5 Mgl and 2-pentanone, followed by hydrolysis
(C) C3H7 Mgl and 2-butanone, followed by hydrolysis
(D) C4H9 Mgl and propanone, followed by hydrolysis

PBr Mg / Et 2O
40. 
3
(X)  (Y)

(A) X is (B) Y is

(C) Z is (D) Z is

41. Consider the structure of given alcohol

The alcohol can be prepared from :

 (A) (B)

(C) (D)

42.

Product(s) C is/are

(A) (B) (C) (D) All the above

43. Matrix of Grignard

Columin I Column II

(i) CH MgBr
(A) 
3
 
 (P) Nucleophilic addition reaction
(ii) H

(i) PhMgBr
(B)    (Q) Electrophilic addition reaction
(ii) H

(i) CH MgBr
(C) 
3
 
 (R) Recemic mixture
(ii) H

(D) PhMgBr(1mole) (S) Nucleophilic substitution reaction

 

(E) PhMgBr(2 mole)

 

44. Reaction
Columin I Column II

LiAlH4
(A) 
H O
 (P) is product
2

3(i) CH MgBr
(B) CH3 – CHO 
(ii) HOH / H

 (Q) CH3 – CH2 – OH is product

(i) CH MgBr
(C) 
3

 (R) Nucleophilic addition reaction
(ii) HOH / H

LiAlH
(D) 
HOH
4
 (S) Electrophilic addition reaction
Single Choice Questions :

1.

Total moles of KOH consumed in this reaction will be

(A) 2 (B) 3 (C) 4 (D) 5

2. KOBr product


Correct stereochemicstry of product will be

(A) (B) (C) (D) A and C both

3. In Hoffman’s Bromamide reaction shifting of alkyl group takes place from

(A) Carbon to Nitrogen (B) Carbon to Carbon
(C) Nitrogen to Carbon (D) Nitrogen to Nitrogen
4. Which of the following compound not undergo Hoffman’s bromamide reaction.

(A) (B) (C) (D)

KOBr
5. (X) 

(A) (B) (C) (D)

6. KOBr (A)


Product will be

(A) Ph – NH2 (B) Ph – NH – CH3 (C) (D)

KOBr CHCl3
7.  (A) 
NaOH
(B)

Product (B) is
(A) Ph – NH2 (B) (C) Ph – N  NH (D) Ph – N = O
 Br2 NH KOBr
8. 
Fe
(A) 

3
(B)  (C)

Product (C) is

(A) (B) (C) (D)

14
Br Mg (1) O  C O NH KOBr
9. 
2
Fe
(A) 
ether
(B)   (C) 

3
(D)  (E)
(2)H

Product (E) is

14
(A) Ph – NH2 (B) Ph – CH2 – NH2 (C) Ph  CH2  NH2 (D) None of these

NH KOBr
10. (A) 

3
(B)  CH3 – NH2

Reactant (A) is

(A) (B)

(C) (D) (A) and (B) both

11. KOBr (A) (B)



Product (B) is

(A) (B)

(C) (D)

12. KOBr (A)



Product (B) is

(A) (B)

(C) (D)
 Br2 KOD
13. 
D2O,
(A) Product (A) is

(A) Ph – NH2 (B) Ph – ND2 (C) Ph – CH2 – NH2 (D) Ph – CH2 – ND2

14. (A)
  R – NH2
Missing reagent (A) is
(A) Br2 + KOH (B) Br2 + HBr (C) Br2 (D) KBr
15. Which of the following will not undergo Hoffmann bromamide reaction ?

(A) (B)

(C) (D) All

16. Most reactive towards Hoffmann bromamide reaction ?

(A) (B) (C) (D)

17. H 
 P
Major product

Identify the structure of ‘P’

(A) (B) (C) (D)

HCl
18. 

 P
major product

Identify the structure of ‘P’

(A) (B) (C) (D)

 
H
19.  P
major product

Identify the structure of ‘P’

(A) (B)

(C) A and B both (D)


H
20.  P
major product

Identify the structure of ‘P’

(A) (B)

(C) A and B both (D)

Ba(OH)2
21.  
 P
major product

Identify the structure of ‘P’

(A) (B) (C) (D)

KOBr
22.  P Identify the structure of ‘P’
major product

(A) (B) (C) (D)

KOBr
23.  P
major product

Identify the structure of ‘P’

(A) (B) (C) (D)

 H2 SO4
24.   P
major product

Identify the structure of ‘P’

(A) (B) (C) (D)

KOBr
25. + NH3 

(A)  (B)

Identify the structure of (B)

(A) (B) (C) (D)

Cl2
26. 
Ca(OH)

 P
2 major product

Identify the structure of ‘P’

(A) CH3 – CN (B) CH3NH2 (C) CH3CH2NH2 (D) CH3–NC

27. Identify C

(A) Ph – CH2 – NH2 (B) Ph – NH2 (C) Ph – CO2H (D) Ph – NH – CH3

NaOBr
28.   (A) ; Product of the reaction is :
(major )

(A) (B) (C) (D)

29. Which of the following reaction represent incorrect major product.

(A) KOBr CH3 – NH2



(i) O2 / h
(B)   
(ii) H3O

NH2 OH H2SO4
(C)  (A) 
(B)
 caprolactum

CH CO H
(D) 3 3
 
30.

Molecular weight of (A) increases by

(A) 80 (B) 82 (C) 84 (D) 86

(1) O2 / h
31.   (A)  (B)
(2) H3O

Product (A) undergoes Reimer Tiemann reaction so the structure of product (B) is

(A) (B) (C) (D)

Question No. 32 to 36 (5 questions)

H2NOH
(A)  

32. Structure of (A) will be

(A) Ph – CHO (B)

(C) ( D) B and C both

33. Structure of (B) will be

(A) (B)

(C) (A) and (B) both (D) None of these

34. Structure of (D) will be

(A) (B)
(C) A and B both (D) None
35. Structure of (F) will be
(A) C2H6NH2 (B) C3H7NH2
(C) CH3NH2 (D) (A) and (B) both
36. Structure of (G) will be
(A) PhCN (B) PhCOOH
(C) PhCHO (D) PhCH3
Questions No. 37 to 39 (3 questions)
HOFFMANN REARRANGEMENT
It involves consversion of a carboxylic acid amide into an amine with a loss of a carbon atom on treatment
with aqueous sodium hypobromite. Thus Hoffmann result in shortening of a carbon chain.

Br2

NaOH
 R – NH2 + NaBr + Ne2CO3

Mechanism of the reaction is

37. , Identify C

Product (A)

(A) Ph – NH2 (B) PH – CH2 – NH2 (C) Ph – NH – CH3 (D)

38. Which of the following will not give Hoffmann bromamide reaction.

(A) (B)

(C) (D)

39. Br2 KOH

  A (Major)

Product (A) is :

(A) (B)

(C) (D)
Question No.40 to 42 (3 questions)
BECKMANN REARRANGEMENT
The given is mechanism of Beckmann rearrangment.

40. Reagent cannot be used in Beckmann rearrangement is

(A) H2SO4 (B) BF3 (C) SO3 (D) HO
41. Rate determining step in the Beckmann rearrangement is
(A) I (B) II (C) III (D) IV

42. H2 SO 4
  (X). product (X) is

(A) (B)

(C) (D)

Questions No. 43 to 45 (3 questions) :

An aromatic compound A react with KOBr to give compound B. Compound B on reaction with chloroform
and KOH gives compound C which possess unpleasant smell. Compound B on reaction with NaNO2 and
HCl followed by reaction with water (boiled) gives compound D. D on reaction with CHCl3 and KOH gives
following compound E

Structure of compound E 

43. Structure of compound A is :

(A) (B) (C) (D)

44. Structure of compound B is :

(A) (B) (C) (D)

45. Structure of compound D is :

(A) (B) (C) (D)

Subjective :

46. (i)

(X) is moles of grignard reagent consumed.

(ii)

(Y) is double bond equivalent (DBE) of product.

(iii)

(Z) is double bond equivalent (DBE) of product.

SO, the value of (X + Y + Z) will be.
47. Identify product of given Beckmann rearrangement :


H
(i) 


Single Choice Questions :
1. Reimer Tiemann reaction is an example of
(A) addition reaction (B) Substitution reaction (C) Elimination reaction (D) Rearrangement reaction

3 CHCl Pot.tert Butoxide

2. cis-3-hexene 


 Major product

(A) cis form (B) trans form (C) achiral (D ) (A) and (C) both
3. In which of the following reaction there is a decrease in carbon atom takes place ?
(A) Isocyanide test (B) Reimertiemann reaction
(C) Hoffman bromamide reaction (D) Beckman rearrangement
4. In which of the following reaction carbene is formed as an intermediate
(A) Isocyanide test (B) Reimer tiemann reaction
(C) Bromination (D) A and B both

5. Major product is

(A) (B) (C) (D)

6. In Reimer Tiemann formylation reaction molecular weight of phenol increases by

(A) 27 (B) 28 (C) 29 (D) 30
7. In Reimer Tiemann reaction medium of reaction is
(A) Acidic (B) Basic (C) Neutral (D) Gas-phase
8. IUPAC name of product formed in Reimer Tiemann formylation will be
(A) 2-hydroxy benzene (B) salicyaldehyde
(C) 2-hydroxy Benzenecarbaldehyde (D) 2-hydroxy Benzenecarboxylicacid
9. Which of the following is electrophile in Reimer Tiemann reaction

Θ
(A) : CCl2 (B) CCl2 (C) PhoH (D) : CH2

NaNO2 H2O CHCl

10. 
2HCl
(A) 
boil
(B)  3
KOH,
(C)

Major product (C) is

(A) (B) (C) (D)

 (1) NaOH
11. + CO2  
 (A)
(2) H
Major product

Structure of product (A) is

(A) (B) (C) (D)

12. IUPAC name of product (A) in questions 11 above is

(A) salicylic acid (B) salicyldehyde
(C) 2-hydroxybenzecarboxylicacid (D) 2-hydroxybenzaldehyde

(1) CO2 ,NaOH

13. Phenol   (A)
(2) H

Product (B) is

(A) (B) (C) (D)

14. IUPAC name of aspirin is

(A) salicylic acid (B) salicyldehyde
(C) 2-acetyllbenzoic acid (D) 2-acetoxybenzoic acid

(1) NaOH
15. + CHCl3   (A)
(2) H

DBE value of (A) is x

moles of RMgX reacts with (A) is (y), sum of (x + y) is
(A) 5 (B) 6 (C) 7 (D) 8
16. The orbital picture of a singlet carbene (:CH2) can be drawn as

(A) (B) (C) (D) none of these

17. The orbital picture of a triplet carbene can be drawn as

(A) (B) (C) (D) none of these

  OH Trans 2butene
18. CHF2Br   (A)   (B)
(Intermediate)
singlet carbene
in this reaction B is

(A) (B) (C) (D)

19. Which of the following will not give carbylamine reaction

(A) t-butyl amine (B) aniline (C) sec. butylamine (D) N-methyl methanamine

(i) CHCl / KOH

20.  3

 (A) Product (A) will be :
(ii) H

(A) (B) (C) (D)

Ph CC Ph EtOK HBr

21. 
EtOK
 A  B  C
correct presentation of C is:

(A) (B) (C) (D)

22. MeOK
  ?

(A) (B) (C) (D)

(i) aq.NaHCO / boil

3
23. 
  (X)
(ii) H3O

Identify unknown (X)

(A) (B) (C) (D)

24. Intermediate produced during reimer tiemann’s formylation will be

(A) :CCl2 (B) :CH2 (C) (D) CHCl3

25. Which of the following compound doesn’t gives Hoffman’s carbyl amine test

(A) (B) (C) (D)

26. CH3 – NH2 + CHCl3 + KOH  major product will be :


(A) CH3 – C  N (B) CH3 – NH – CH3 (C) CH3  N  C (D) NH3

27. What is the product of the following reaction ?

MeOK in chloroform
  ?

(A) (B) (C) (D)

(i) CHCl NaOH

28. 
3
  P
(ii) H major product

Identify the structure of ‘P’

(A) (B) (C) (D)

(i) CHCl NaOH

29. 
3
  P
(ii) H major product

Identify the structure of ‘P’

(A) (B) (C) (D)

(i) CHCl NaOH

30. 
3
  P
(ii) H major product

Identify the structure of ‘P’

(A) (B) (C) (D)

 CHIClBr
31. 
KOH
 P
major product

Identify the structure of ‘P’

(A) (B) (C) (D)

32. + CHCl3 + KOH  major Pproduct

Identify the structure of ‘P’

(A) (B) (C) (D)

33. R – NH2 + x  KOH

 R–
Structure of x in given reaction will be
(A) CCl4 (B) CHCl3 (C) CH2Cl2 (D) CH4

34.

Correct order of yield of products A & B is

(A) A > B (B) B > A (C) A = B (D) B >> A
Question NO. 35 to 37 (3 questions)
It is belived that chloroform andb hydroxide ion react to produce an electron dificient intermediate dichloro
carbene : CCl2(DCC)

Treatment of phenol with DCC in basic medium interduces an aldehyde group, onto the aromatic ring. This
reaction is known as Reimer Tiemann reaction.

The reimer–Tiemann reaction involves electrophilic substitution on highly reactive phenoxide ring. The
electrophilic reagent is dichloro carbene : CCl2

o-prooduct is major product because :

 (i) there are two o-positions available as compared to one para.
(ii) o-product is more stable due to the formation of six membered chelate formation.

Mechanism of lsocyanide test :

If 1° amines (aliphatic and aromatic) react with DCC in basic medium it yield isocyanide of carbyiamine. This
reaction is known as carbylamine reaction :
The product is known as isocyanide & it is a foul smelling substance.

35. Step marked by  is

(A) Aromatization reaction (B) Intramolecular acid base reaction
(C) Both of the above (D) None of the above

36. If is used instead of 74 during Rimer Tiemann reaction the product formed is:

(A) (B) (C) (D)

37. If CCl4 is used in place of CHCl3 during Reimer Tiemann reaction, the product formed is:

(A) (B) (C) (D)

38.

Statement-1 : Carbocation is formed.

Statement-2 : Loss of water is followed by NH2 – CH3 attack.
Statement-3 : The transition state is sp3 hybridised
Statement-4 : An oxime is one of the possible products.
Which of the above statements is/are not true?
(A) 4 (B) 3 (C) 2 (D) 1
39.

Choose the correct product(s)

(A) Schiff’s base (B) Brady’s reagent (C) (D)

40.

A, B and C respectively are:

The final product (C) contains which of the following functional groups
(A) Alcohol (B) Ketone (C) Carboxylic (D) Ester
41. Match the following :
Columin I Column II


H
(A) 

 (P) An enamine will form

(B) (Q) Schiff base will form

(C)  (R) Hydrazone will form

(D) + NH2 – NH2  (S) product form will undergo Lassigne test

(i) KCN
42.  
 ‘P’
(ii) H3O

Find oout the incorrect statement about the above given reaction
(A) It is a nucleophilic addition reaction
(B) Obtained product is present in reacemic mixture
(C) They hydrolysis of obtained product given -hydroxy acid
(D) It is a electrophilic addition reaction
 NaNO2 H2O
43. 
2HCl
(A) 
boil
(B)

Product (B) will be :

(A) (B) (C) (D)

 PART-1
* Marked Questions are more than one correct options.
1. Acetamide is treated separately with the following regents. Which of these would give methylamine ?
[JEE 1983]
(A) PCl5 (B) Sodalime (C) NaOH + Br2 (D) Hot, conc. H2SO4
2. Carbylamine test is performed in alc. KOH by heating a mixture of [JEE 1984]
(A) chloroform and silver powder
(B) trihalogenated methane and a primary amine
(C) an alkyl halide and a primary amine
(D) an alkyl cyanide and a primary amine
3. Alcoholic solution of KOH is a specific reagent for – [IIT 1990]
(A) Dehydration (B) Dehydrogenation
(C) Dehydro halogenation (D) Dehalogenation

4. The formation of cyanohydrin from a ketone is an example of : [IIT 1990]

(A) Electrophilic additon (B) Nucleophilic addition
(C) Nucleophilic substitution (D) Electrophilic substitution

5. An organic compound C3H6O does not give a precipitate with 2, 4-Dionitrophenyl hydrazine reagent and
does not react with metallic sodium. It could be : [IIT 1993]
(A) CH3CH2CHO (B) CH3COCH3
(C) CH2 = CH – CH2OH (D) CH2 = CH – O–CH3

6. Which of the following carboylic acids undergoes decarboxylation easily ? [IIT 1995]
(A) C6H5COCH2COOH (B) C6H5COCOOH
(C) C6H5CH(OH)COOH (D) C6H5CH(NH2)COOH

7. Among the given compounds, the most susceptible to nucleophilic attack at the carbonyl group is
[IIT 1996]
(A) MeCOCl (B) MeCHO
(C) MeCOOMe (D) MeCOOCOMe

8. (CH3)3CMgCl on reaction with D2O produces [IIT 1996]

(A) (CH3)3 CD (B) (CH3)3 COD (C) (CD)3 CD (D) (CD)3 COD

9. CH3CHO + H2NOH  CH3 – CH = N – OH. The above reaction occurs at: [IIT 1997]
(A) pH = 1 (B) pH = 4.5
(C) Any value of pH (D) pH = 12

10. When cyclohexane is poured on water, it floats, because – [IIT 1997]

(A) Cyclohexand is in ‘boat’ form (B) Cyclohexane is in ‘chair’ form
(C) Cyclohexane is in ‘crown’ form (D) Cyclohexane is less dense than water

11. Among the following compounds, which will react with acetone to give a product containing >?
[IIT 1998]
(A) C6H5NH2 (B) (CH3)3N
(C) C6H5NHC6H5 (D) ClCH2CH2Cl
12. Which of the following will react with water : [IIT 1998]
(A) CHCl3 (B) Cl3CCHO
(C) CCl4 (D) ClCH2CH2Cl

13. A new carbon-carbon bond formation is possible in [JEE 1998]

(A) wolf-kishner reduction (B) Friedel-Craft alkylation
(C) Clemmensen reduction (D) Reimer-Tiemann reaction

14. A positive carbylamine test is given by [JEE 1999]

(A) N, N-dimethylaniline (B) 2, 4-dimethylaniline
(C) N-methyl-o-methylaniline (D) p-methylbenzylamine

15. Compound A (molecular formula C3H8O) is treated with acidified potassium dichromate to form a product B
(molecular formula C3H6O). B forms a shining silver mirror on warming with ammonical silver nitrate. B when
treated with an aqueous solution of H2NCONHNH2. HCl and sodium acetate gives a product C. Identify the
structure of C. [IIT 2002]

(A) CH3CH2CH = NNHCONH2 (B)

(C) (D) CH3CH2CH = NCONHNH2

16. Identify the correct order of boiling point of the following compounds : [IIT 2002]
CH3CH2CH2CH2OH CH3CH2CH2CHO CH3CH2CH2COOH
1 2 3
(A) 1 > 2 > 3 (B) 3 > 1 > 2 (C) 1 > 3 > 2 (D) 3 > 2 > 1

17. What would be the major product in the following reaction ? [JEE-2000, 1/100]

H2
  
Lindlar catalyst

18. The appropriate reagent for the following transformation: [JEE-2000, 1/100]

(A) Zn (Hg), HCI (B) NH2NH2, OH– (C) H2/Ni (D) NaBH4

19. What would be the major product in each of the following reactions? [IIT 2000]

CH 3
| C2 H5OH H
2
(i) CH 3  C  CH 2 Br   (ii) 
 Lindlar's Catalyst
|
CH 3
20. Identify X and Y in the following synthetic scheme and write their structures. Explain the formation of labelled
* ) as one of the products when compound (Z) is treated with HBr and subsequently
formaldehyde ( H2CO
*
ozonolysed. Mark the radioactive carbon in the entire scheme. X is obtained by heating of Ba C O3 with
H2SO4.

(i) Mg / ether LiAlH4

CH2 = CH — Br       Y    Z [JEE-2001, 5/100]
(ii) X
(iii) H3O 

21. CH3MgI is an organometallic compound due to : [AIEEE-2002]

(1) Mg – I bond (2) C – I bond (3) C – Mg bond (4) C – H bond

22. But-1-ene may be converted to butane by reaction with : [AIEEE-2003]

(1) Zn – HCl (2) Sn – HCl (3) Zn – Hg (4) Pd / H2

CH3MgBr
23. Ethylester     P. The product P will be [JEE-2003, 3/84]
excess

(A) (B) (C) (D)

CH MgBr CH MgBr
24.  
3

  
3

 H O
3 

25. The number of chiral compounds produced upon monochlorination of 2-methylbutane is :

[JEE-2004, 3/84]
(A) 2 (B) 4 (C) 6 (D) 8

26. Which one of the following is reduced with Zn/Hg and hydrochloric acid to give the corresponding hydrocarbon
[AIEEE-2004]
(1) Ethyl acetate (2) Acetic acid (3) Acetamide (4) Butanone

27. The order or reactivity of phenyl magnesium bromide with the following compounds is : [JEE-2004, 3/84]

(A) (II) > (III) > (I) (B) (I) > (III) > (II) (C) (II) > (I) > (III) (D) all react with the same rate

28. 2-Methylbutane on reacting with bromine in the presence of sunlight gives mainly [AIEEE-2005]
(1) 1-Bromo-3-methylbutane (2) 1-Bromo-2-methylbutane
(3) 2-Bromo-3-methylbutane (4) 2-Bromo-2-methylbutane

29. When Phenyl Magnesium Bromide reacts with tert. butanol, which of the following is formed?
(A) Tert. butyl methyl ether (B) Benzene
(C) Tert. butyl benzene (D) Phenol [IIT ‘2005]
30. 1–bromo–3–chlorocyclobutane when treated with two equivalents of Na, in the presence of ether which of the
following will be formed? [IIT ‘2005]

(A) (B) (C) (D)

31. 1-Bromo-3-chlorocyclobutane will react with two moles of Na in ether producing [JEE-2005, 3/60]

(A) (B) (C) (D)

32. Phenyl magnesium bromide reacting with t-Butyl alcohol gives [JEE-2005, 3/60]

(A) Ph – OH (B) Ph – H (C) (D)

33. The smallest ketone and its next homolgue are reacted with NH2OH to form oxime. [IIT 2006]
(A) Two different oximes are formed (B) Three different oximes are formed
(C) Two oximes are optically acitve (D) All oximes are optically acitve

34. CH3NH2 + CHCl3 + KOH  Nitrogen containing compound + Cl + H2O. Nitrogen containing compound is
[JEE 2006]
  
(A) CH3CN (B) CH3NHCH3 (C) CH3 – N  C (D) CH3 – N  C

Cl / h Fractional
35. (CH3)2CH – CH2CH3 2 [N]     [P] [JEE-2006, 5/184]
distillati on

The number of possible isomers [N] and number of fractions [P] are
(A) (6, 6) (B) (6, 4) (C) (4, 4) (D) (3, 3)

Comprehension (Q. No. 36 to 38)

Riemer-Tiemann reaction introduces an aldehyde group, on to the aromatic ring of phenol, ortho to the hydroxyl
group. This reaction involves electrophilic aromatic substitution. This is a general method for the synthesis of
substituted salicylaldehydes as depicted below.

OH ONa OH
CHO aq. HCl CHO
[]
(Intermediate)

CH3 CH3 CH3

() () ()

36. Which one of the following reagents is used in the above reaction ? [JEE 2007, 4/162]
(A) aq. NaOH + CH3Cl (B) aq. NaOH + CH2Cl2
(C) aq. NaOH + CHCl3 (D) aq. NaOH + CCl4

37. The electrophile in this reaction is : [JEE 2007, 4/162]

+ •
(A) :CHCl (B) CHCl2 (C) :CCl2 (D) CCl3
38. The structure of the intermediate  is : [JEE 2007, 4/162]

O Na  
O Na  
O Na 
ONa
CH2Cl CHCl2 CCl3 CH2OH

(A) (B) (C) (D)

CH3 CH3 CH3 CH3

39. The treatment of CH3MgX with CH3CC–H produces [AIEEE-2008]

(1) CH3CC–CH3 (2) (3) CH 4

(4) CH3–CH=CH2

Comprehension -1
In the following reaction sequence, product I, J and L are formed. K represents a reagent.
[JEE-2008, 12/163]

Hex-3-ynal I J L

40. The structure of the product I is ; [JEE-2008, 4/163]

(A) (B)

(C) (D)

41. The structures of compound J and K, respectively, are : [JEE-2008, 4/163]

(A) and SOCl2 (B) and SOCl2

(C) (D) and CH3SO2Cl

42. The structure of product L is : [JEE-2008, 4/163]

(A) (B)

(C) (D)

43. Match each of the compounds in Column I with its characteristic reaction(s) in Column II.
[JEE-2009, 8/160]
Column I Column II
(A) CH3CH2CH2CN (p) Reduction with Pd-C/H2
(B) CH3CH2OCOCH3 (q) Reduction with SnCl2/HCl
(C) CH3–CH=CH–CH2OH (r) Development of foul smell on treatment with
chloroform and alcoholic KOH.
(D) CH3CH2CH2CH2NH2 (s) Reduction with diisobutylaluminium hydride (DIBAL-H)
(t) Alkaline hydrolysis

44. 2-Hexyne gives trans - 2 - Hexene on treatment with : [AIEEE-2012, 4/120]

(1) Pt/H2 (2) Li/NH3 (3) Pd/BaSO4 (4) LiAlH4
45. In the given transformation, which of the following is the most appropriate reagent ? [AIEEE-2012, 4/120]

(1) NH2 NH2, (2) Zn – Hg/HCl (3) Na, Liq. HCl (4) NaBH4

46. In the following reaction, the product(s) formed is(are)

? [Aromatic Compounds] [JEE-2013_Advanced-P-2]

P Q R S
(A) P (major) (B) Q (minor) (C) R (minor) (D) S (major)

Paragraph for Question Nos. 19 to 20

P and Q are isomers of dicarboxylic acid C4H4O4. Both decolorize Br2/H2O. On heating, P forms the cyclic
anhydride.
Upon treatment with dilute alkaline KMnO4, P as well as Q could produce one or more than one from S, T
and U. [JEE Advanced_2013]

S T U
47. In the following reaction sequences V and W are, respectively :
H2 / Ni
Q 
 V

(A) and (B) and

V W V W

(C) and (D) and

V W V W
48. Compounds formed from P and Q are, respectively :
(A) Optically active S and optically active pair (T, U)
(B) Optically inactive S and optically inactive pair (T, U)
(C) Optically active pair (T, U) and optically active S
(D) Optically inactive pair (T, U) and optically inactive S

49. Among P, Q, R and S, the aromatic compound(s) is/are : [Aromatic Compound]

[JEE-2013_Advanced-P-1]

(A) P (B) Q (C) R (D) S

50. The major product in the following reaction is [JEE Advance 2014]
[Figure]

(A) (B)

(C) (D)

51. Compound(s) that on hydrogenation produce(s) optically inactive compound(s) is (are)

[JEE Advance 2015]

(A) (B)

(C) (D)

52. Reagent(s) which can be used to bring about the following transformation is (are) [JEE Advance 2016]

(A) LiAlH4 in (C2H5)2O (B) BH3 in THF

(C) NaBH4 in C2H5OH (D) Raney Ni/H2 in THF
1. Write blanced equations for the following reaction : [JEE 1983]
“Acetamide is reacted with bromine in the presence of potassium hydroxide.”

2. Complete the following with appropriate structures : [JEE 1986]

3. Conversion
Pheenol to aspirin

4. 
+ t-BuOK   major product

Structure of major product is [JEE 1994]

5. Complete the following, giving the structures of the principal organic product : [JEE 1997]


+ CHBr3 + t-BuOK  

6. There is a solution of p-hydroxybenzoic acid p-amine benzoic acid. Discuss one method by which we can
separate them and also write down the confirmatory test of the functional group present. [IIT-JEE 2003]

GRIGNARD REAGENT & ITS APPLICATION

7. Write the structural formula of the main organic product formed when ethyl acetate is treated with double
the molar quantity of methyl magnesium bromide and the reaction mixture is poured into water. [IIT 1981]

8. State the conditions under which the following preparation is carried out. “Aniline from benzene”
[JEE 1983]
9. Arrange the following in order of their increasing reactivity towards HCN / RMgX [IIT 1985]
CH3CHO, CH3COCH3, HCHO, C2H5COCH3

10. Identify the major product in the following reactions : [IIT 1993]
C6H5COOH + CH3MgI  ? + ?

11. Predict the major product in the following reaction : [IIT 1994]
(i) CH MgBr(excess)
C6H5CH2CO2CH3 
3
(ii) H


12. Acetophenone on reaction with hydroxylamine-hydrochloride can produce two isomeric oximes. Write
structures of the oximes. [IIT 1997]

13. The total number of carboxylic acid groups in the product P is [JEE ADVANCE : 2013]
 PART-2
Single Choice Questions :

1. The compound is used as [AIEEE-2002]

(A) antiseptic (B) antibioitic (C) analgesic (D) pesticidie

2. When primary amine reacts with chloroform in ethanoic KOH then the product is [AIEEE-2002]
(A) an isocynide (B) an aldehyde (C) a cyanide (D) an alcohol

3. The reaction of chloroform with alchoholic KOH and p-touidine form [AIEEE-2003]

(A) (B)

(C) (D)

4.

The electrophile involved in the a bove reaction is [AIEEE-2006]

(A) dichloromethyl cation (B) dichlorocarbene (: CCl2)

(C) trichloromethyl anion (D) formyl cation

5. In the chemical reaction,

CH3CH2NH2 + CHCl3 + 3KOH  (A) + (B) + 3H2O, the compound (A) and (B) are respectively
(A) C2H4CN and 3KCl (B) CH3CH2CONH2 and 3KCl [AIEEE-2007]
(C) C2H5NC and K2CO3 (D) C2H5NC and 3KCl

6. The major product obtained on interaction of phenol with sodium hydroxide and carbon dioxide is :
[AIEEE-2009]
(A) salicyclic acid (B) pthalic acid
(C) benzoic acid (D) salicyaldehyde

7. Aspirin is known as : [AIEEE-2012]

(A) Acetyl salicylic acid (B) Phenyl salicylate
(C) Acetyl salicylate (D) Methyl salicylic acid

8. An organic compound A upon reacting with NH3 givesv B. On heating, B gives C. C in presence of KOJH
reacts with Br2 to give CH3CH2NH2.A is : [AIEEE-2013]
(A) CH3CH2COOH (B) CH3COOH

(C) CH3CH2CH2COOH (D)

9. The reaction of phenol with benzoykl chloride to give phenyl benzoate is known as :
[IIT-JEE Mains (Online) 2013]
(A) Schotten - Baumann reaction (B) Reimer - Tiemann reaction
(C) Claisen reaction (D) Gatterman-Koch reaction

10. Phenol on heating with CHCl3 and NaOH gives salicylaldehyde. The reaction is called :
[IIT-JEE Mains (Online)2013]
(A) Claisen reaction (B) Hell - Volhard - Zelinsky reaction
(C) Cannizzaro’s reaction (D) Reimer - Tiemann reaction

11. Carbylamine forms from aliphatic or aromatic primary amine via which of the following intermediates ?
[IIT-JEE Mains (Online)2013]
(A) Carbene (B) Carbon radical
(C) Carbo cation (D) Carbanion

GRIGNARD REAGENT & ITS APPLICATION

12. Which of these will not react with acetylene ? [AIEEE-2002]

(A) NaOH (B) ammonical AgNO3 (C) Na (D) HCl

13. Ethyl isocyanide on hydrolysis is acidic medium generates [AIEEE-2003]

(A) ethylamine salt and methanoic acid (B) propanoic acid and ammonium salt
(C) ethanoic acid and ammonium salt (D) methylamine salt and ethanoic acid

14. When CH2 = CH – COOH is reduced with LiAlH4, the compound obtained will be [AIEEE-2003]
(A) CH3 – CH2 – COOH (B) CH2 = CH – CH2OH
(C) CH3 – CH2 – CH2OH (D) CH3 – CH2 – CHO

15. Rate of the reaction [AIEEE-2004]

is fastest when Z is
(A) Cl (B) OCOCH3 (C) OC2H5 (D) NH2

16. Acetyl bromide reacts with excess of CH3Mgl followed by treatment with a saturated solution of NH4Cl given
[AIEEE-2004]
(A) acetone (B) acetyl iodide
(C) 2-methyl-2-propanol (D) acetamide

17. Reaction of cyclohexanone with dimethylamine in the presence of catalytic amount of an acid forms a
compound if water during the reaction is continuously removed. The compound formed is generally known
as [AIEEE-2005]
(A) a Schiff’s base (B) an enamine (C) an imine (D) an amine

18. The increasing order of the rate of HCN addition to compounds A – D is [AIEEE-2006]
(I) HCHO (II) CH3COCH3 (III) PhCOCH3 (IV) PhCOPh
(A) I > II > III > IV (B) II > I > III > IV (C) III > IV > I > II (D) IV < III < II < I
19. Phenyl magnensium bromide reacts with methanol to give [AIEEE-2006]
(A) a mixture of anisole and Mg (OH)Br (B) a mixture of benzene and Mg(OMe)Br
(C) a mixture of toluene and Mg(OH)Br (D) a mixture of phenol and Mg(Me)Br

20. In the following sequence of reactions. [AIEEE-2007]

P IMg HCHO HO
CH3CH2OH 
2
 A 
ether
B   C 
2
D

the compound ‘D’ IS

(A) butanal (B) n-butyl alcohol (C) n-propyl alcohol (D) propanal

21. Which of the following is the strongest base in aqueous solution ? [AIEEE-2008]
(A) Trimethylamine (B) Aniline (C) Dimethylamine (D) Methylamine

22. The treatment of CH3MgX with CH3C  C –H produces [AIEEE-2008]

(A) CH3CH = CH2 (B) CH3C  C – CH3 (C) (D) CH4

23. In the chemical reactions,

the compounds ‘A’ and ‘B’ respectively are [AIEEE-2010]

(A) benzene diazonium chloride and fluorobenzene
(B) nirobenzene and chlrobenzene
(C) nitrobenzene and fluorobenzene
(D) phenol and benzene

24. Aryl fluroride may be prepared from arene diazonium chloride using : [IIT-JEE Mains (Online)2013]
(A) HBF4/NaNO2, CU,  (B) CuF/HF
(C) Cu/HF (D) HBF4/

25. A major component of Borsch reagent is obtained by reacting hydrazine with which of the following with
which of the following ? [IIT Mains Online 2013]

(A) (B) (C) (D)

26. Cleammensen reduction of a ketone is carried out in the presence of : [IIT Mains Online 2013]
(A) Glycoal with KOH (B) Zn - Hg with HCl (C) LiAlH3 (D) H2with Pt as catalyst

27. Which of the following reagent(s) used for the conversion ? [IIT Mains Online 2013]



(A) glycol/NaH/H2O+ (B) LiAlH4 (C) NaBH4 (D) glycol/LiAlH4/H3O+

28. Which one of the following reactions will not result in the formation of carbon bond ?
(A) Reimer-Tieman reaction (B) Friedel Craft’s acylation
(C) Wurtz reaction (D) Cannizzaro reaction
 EXERCISE-1
1. (D) 2. (C) 3. (D) 4. (A) 5. (B) 6. (D) 7. (D)
8. (C) 9. (C) 10. (A) 11. (C) 12. (B) 13. (D) 14. (C)
15. (B) 16. (B) 17. (C) 18. (B) 19. (B) 20. (A) 21. (A)
22. (B) 23. (A) 24. (B) 25. (A) 26. (C) 27. (ACD) 28. (A)
29. (C) 30. (B) 31. (C) 32. (D) 33. (C) 34. (A) 35. (D)
36. (BC) 37. ABCD 38. ABC 39. ABC 40. ABC 41. ABC 42. AB
43. A – P ; B – P, R; C – P ; D – S ; E – P, S
44. A  P, R ; B  P, R; C  Q, R ; D – R

EXERCISE-2
1. (C) 2. (D) 3. (A) 4. (D) 5. (A) 6. (A) 7. (B)
8. (A) 9. (A) 10. (D) 11. (A) 12. (D) 13. (B) 14. (A)
15. (D) 16. (B) 17. (A) 18. (A) 19. (B) 20. (A) 21. (B)
22. (B) 23. (D) 24. (C) 25. (D) 26. (B) 27. (D) 28. (A)
29. (A) 30. (C) 31. (B) 32. (B) 33. (A) 34. (A) 35. (C)
36. (B) 37. (A) 38. (D) 39. (D) 40. (D) 41. (B) 42. (A)
43. (C) 44. (D) 45. (B) 46. 13 47.

EXERCISE-3
1. (B) 2. (D) 3. (C) 4. (D) 5. (B) 6. (B) 7. (B)
8. (C) 9. (A) 10. (B) 11. (A) 12. (C) 13. (D) 14. (D)
15. (C) 16. (A) 17. (C) 18. (C) 19. (D) 20. (C) 21. (C)
22. (A) 23. (B) 24. (A) 25. (A) 26. (C) 27. (C) 28. (D)
29. (B) 30. (C) 31. (A) 32. (B) 33. (B) 34. (A) 35. (C)
36. (A) 37. (D) 38. A 39. BC 40. ABC
41. A  P, S ; B  Q, S; C  Q, S ; D  R, S 42. D 43. A
EXERCISE-4
1. (C) 2. (B) 3. (C) 4. (B) 5. (D) 6. (A) 7. (A)
8. (A) 9. (B) 10. (D) 11. (A) 12. (B) 13. (B,D) 14. (BD)
15. (A) 16. (B)
17. In presence of lindlar’s catalyst (Pd and CaCO3) in quinoline) partial hydrogenation takes place and give
cis-isomer.

H2
  
Lindlar catalyst

CH 3
|
18. (B) 19. (i) CH 3  C  CH 2  CH 3 (ii)
|
O  C2H6

(i ) Mg / ether ( ii) C O 2
20. CH2 = CH – Br    CH2 = CH – Mg – Br  


(iii) H3O LiAlH 4
   
– Mg( OH)Br
21. (C) 22. (D) 23. (A)
24. (*) 25. (B) 26. (D) 27. (C) 28. (D) 29. (B)
30. (D) 31. (A) 32. (B) 33. () 34. (D) 35. (B)
36. (C) 37. (C) 38. (B) 39. (C) 40. (D) 41. (A) 42. (C)
43. (A) – p, q, s, t ; (B) – s, t ; (C) – p ; (D) – r 44. (B) 45. (A) 46. (B)
47. (A) 48. (B) 49. (A,B,C,D) 50. (D) 51. (BD)
52. (CD)
EXERCISE-5
1. CH3CONH2 + Br2 + 4NaOH CH3NH2 + Na2CO3 + 2NaBr + 2H2O

2.

3. (i)

4. Ph  C  C  Ph 5.
6.

7. Esters when treated with Grignard reagents followed by hydrolysis form ketones. Ketones react further with
excess Grignard reagent followed by hydrolysis to form teritary alcohols.

8.

9. Steric hindrance at carbonyl carbon determine the reactivity twoards nucleophilic addition reaction. Greater
the steric hindrance, smaller the reactivity.
C2H5COCH3 < CH3COCH3 < CH3CHO < HCHO
10. C6H5COOH + CH4MgI  CH4 + C6H5COOMgBr
11.

12.

13. 2

PART-2
1. (C) 2. (A) 3. (D) 4. (B) 5. (D) 6. (A) 7. (A)
8. (A) 9. (A) 10. (D) 11. (A) 12. (A) 13. (A) 14. (B)
15. (A) 16. (C) 17. (B) 18. (D) 19. (B) 20. (C) 21. (C)
22. (D) 23. (A) 24. (D) 25. (D) 26. (B) 27. (D) 28. (D)