ORGANIC REACTION MECHANISMS-I

CONTENTS
Particular Page No.

Theory 01 – 08
Exercise - 1 09 – 14
Part - I : Subjective Questions

EX
Part - II : Only One Option Correct Type
Part - III : Match the Columns
Exercise - 2 14 – 20
Part - I : Only One Option Correct Type
Part - II : Single or Double Digit Integer Type Questions
Part - III : One or More Than One Options Correct Type
Part – IV : Comprehensions
Answers 21 – 22
Additional Problems for Self Practice (APSP) 23 – 33
Part - I : PRACTICE TEST-1 (IIT-JEE (MAIN Pattern))
D
Part - II : NATIONAL STANDARD EXAMINATION IN CHEMISTRY (NSEC) STAGE-I
Part – III : PRACTICE TEST-2 (IIT-JEE (ADVANCED Pattern))
APSP Answers 34
APSP Solutions 34 – 37
O
JEE(Advanced) Syllabus

Aldehydes and Ketones : Nucleophilic addition reactions (Grignard addition).

Carboxylic acids: Formation of esters, acid chlorides, amides and ester hydrolysis.

JEE(Main) Syllabus
C

Aldehydes and Ketones : Nature of carbonyl group, Nucleophilic addition to >C=O group, relative
reactivities of aldehydes and ketones, Important reactions such as Nucleophilic addition reactions
(addition of HCN and Grignard reagent).
Carboxylic Acids : Chemical properties.

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 Organic Reaction Mechanisms-I

Section (A): Electrophile, Nucleophile, Nucleophilicity, Leaving group ability &

Solvent
An organic reaction can be represented as
solvent
Reactant (substrate) + Reagent   Product

Types of bond dissociation :

All reactions are initiated with bond dissociation. There are two types of bond dissociation.
(a) Homolytic bond dissociation : A bond dissociation in which a bond pair electron is equally distributed

EX
to the bonding atoms.
e.g., A–B  A• + B•
A homolytic bond dissociation generates radicals.
(b) Hetrolytic bond dissociation : A bond dissociation in which a bond pair electron is shifted to one atom
only.
e.g., A–B  A + B
A hetrolytic bond dissociation always generate a cation and an anion.
Types of reagents :
A reagent generates three type of attacking species. Which are :
(a) Electrophiles (b) Nucleophiles (c) Radicals
(a) Electrophiles : Electrophiles are electron deficient species. Which can accept a pair of electron.
    
D
e.g. H , Cl, Br, NO2 , CH3 (positively charged species), PCl5, SO2, SO3 BH3(species with vacant orbital
at central atom) carbenes etc.
(b) Nucleophiles : Nucleophiles are electron rich species having atleast one unshared pair of electron. It
can be neutral or negativetely charged. It is always a lewis base.
e.g. CN–, OH–, Br – , I – , NH3 , etc.

(c) Radicals : It is an electron deficient species with odd electron around an atom.
O
e.g. CH3 , C2H5, C2H5O, CH3COO, X etc.

Nucleophilicity :
The tendency to give e– pair to an electron deficient carbon atom is defined as nucleophilicity.
(i) Criteria for Nucleophilicity :
1. The factors which increases e– density at donor atom increases nucleophilicity.
2. The more polarisable donor atom is the better nucleophile. Therefore size of donor atom increases
nucleophilicity also increases.
C

(ii) Periodicity :
Nucleophilicity decreases from left to right in a period.

 In a group, nucleophilicity increases from top to bottom because size of donor atom increases but
basicity decreases from top to bottom.
Acidic strength : HI > HBr > HCl > HF
Basic strength : F¯ > Cl¯ > Br¯ > I¯
Nucleophilicity : F¯ < Cl¯ < Br¯ < I¯
(iii) Nucleophilicity of halogenes in polar aprotic solvents : F¯ > Cl¯ > Br¯ > I¯

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 Organic Reaction Mechanisms-I

(iv) Steric effects on nucleophilicity

(a) (b)

Note : Because (a) can not approach to carbon atom easily.

So, nucleophilicity order is : (b) > (a) and basicity order is : (a) > (b)
Ambident nucleophile :
The species which have more than one nucleophilic site for reaction are called ambident nucleophiles.
Example : CN ,NO2 ,O CH S
Comparision between Nucleophilicity & Basicity :

EX
Nucleophilicity Basicity Remarks
If donor atoms belong to
same period, then
1 CH3¯ > NH2¯ > OH¯ > F¯ CH3¯ > NH2¯ > OH¯ > F¯
nucleophilicity and basicity
order is same
2 SiH3¯ > PH2¯ > SH¯ > Cl¯ SiH3¯ > PH2¯ > SH¯ > Cl¯ " " "
Down the group nucleophilicity
3 F¯< Cl¯ < Br¯ < I¯ F¯> Cl¯ > Br¯ > I¯ increases while basicity
decreases.
" " "" "
4 OH¯ < SH¯ OH¯ > SH¯ "
5 RO¯ < RS¯ RO¯ > RS¯ " " "
If donor atom is same, then
6 RO¯ > HO¯ Same generally nucleophilicity and
basicity order is also same.
D
7 RCOO– < PhO¯< HO¯ < RO¯ Same " " "

>
8 Same " " "

Tetrahedral (more extensive resonance)

[d–p bonds]
O
9 HO¯ > H2O Same
10 NH2¯ > NH3 Same
11 CF3SO3¯ < PhCOO¯ < PhO¯ < RO¯ Same
Leaving group ability/Nucleofugality :
Weaker bases are always good leaving groups / nucleofuse. A good leaving group always stabilize
the transition state and lowers its energy of activation hence increases the rate of the reaction.
C

(a) Order of leaving group ability.

1. > > > 2. CH3¯ < NH2¯ < OH¯ < F¯
3. R–COO¯ > PhO¯ > HO¯ > RO¯ 4. SH¯ > OH¯

5. >

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 Organic Reaction Mechanisms-I

6. Other good leaving groups are

Note : (i) Strong bases rarely act as leaving group 

(Strong base / poor leaving group)

(It is not a leaving group)

(ii) The leaving group should have lower bond energy with carbon.

EX
(iii) Negative charge should be more stable either by dispersal or declocalization.
Types of solvents :
(a) Non polar solvents
(b) Polar solvents (i) polar protic (ii) polar aprotic
(i) Polar protic : A polar solvent which has acidic hydrogen.
(ii) Polar aprotic : A polar solvent which does not have acidic hydrogen.
Solvents Polar Protic Aprotic Remarks
1. H2O   – Polar protic solvent
2. CH3OH   – Polar protic solvent
3. CH3CH2OH   – Polar protic solvent
4. H–COOH   – Polar protic solvent
5. CH3–COOH   – Polar protic solvent
D
6. NH3   – Polar protic solvent

7.  ×  Polar aprotic solvent

 ×  Polar aprotic solvent

O
8.

9.  ×  Polar aprotic solvent

10.  ×  Polar aprotic solvent

C

11.  ×  Non-polar solvent

12.   ×  Non-polar solvent

13. CH3–CH2–CH2–CH2–CH3  ×  Non-polar solvent

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 Organic Reaction Mechanisms-I

Section (B) : Types of organic reactions and reactions of acidic hydrogen

Compounds having reactive or acidic hydrogen gives acid base reaction.
(i) Reaction with metals : CH3COOH + Na  CH3COONa + ½ H2
(ii) Reaction with alkalies : CH3COOH + NaOH CH3COONa + H2O
(iii) Reaction with bicarbonates : CH3COOH + NaHCO3 CH3COONa + CO2 + H2O
(iv) Reaction with NaH : CH3COOH + NaH  CH3COONa + H2
(v) Reaction with Grignard reagent :
R–MgBr + Z–H R–H + Mg(Br)Z
R–MgBr + H–OH R–H + Mg(Br)OH
R–MgBr + H–NHR'R–H + Mg(Br)NHR'
R–MgBr + H–C  C–R' R–H + Mg(Br)C  C–R'
O O

EX
R–MgBr + H O C R R–H + Mg(Br)O C R
H
R–MgBr + R–H + Mg(Br)
H
Section (C) : Nucleophilic addition reactions of carbonyl compounds
It is a characteristic reaction of carbonyl compounds (aldehydes and ketones).
This reaction involves addition of a nuceophile and a electrophile across the (C=O) double bond.
The general nucleophilic addition reaction can be represented as followed :
 
E Nu


The mechanism can be carried out in following two manners.

(a) Acid catalysed (first attack is of electrophile)
D
(b) Base catalysed (first attack is of nucleophile)
O
Acid catalysed nucleophilic addition is generally faster than base catalysed.
The reactivity of the carbonyl group arises from the electronegativity of the oxygen atom and the
resulting polarization of the carbon-oxygen double bond. The electrophilic carbonyl carbon atom is sp2
hybridized and flat, hence it is relatively unhindered and open to attack from either face of the double
bond.
Reactivity : Aldehydes are more reactive than ketones in nucleophilic addition reactions.
R
C

> C=O >

H

There are two factors which influence the reactivity of ketone and aldehyde.
(i) Inductive effect (ii) steric factor
(i) + I effect of alkyl group decrease the amount of charge on C+ (C+–O–) in ketones.
(ii) Steric effect also causes the less reactivity of carbonyl group.

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 Organic Reaction Mechanisms-I

(i) Addition of hydrogen cyanide (HCN)

HCN + OH—

Note : (i) Addition of HCN over aldehyde and ketones gives cyanohydrin.
(ii) Cyanohydrin on acid hydrolysis gives -hydroxy acid.
(iii) Cyanohydrin on treating with NH3(l) followed by acid hydrolysis gives -amino acid.
(iv) In case of ketone cyanohydrin formation is reversible due to bulky groups of ketone which hinder
the formation.

EX
NaCN
e.g. CH3 CHO  H SO
 CH3 CH CN
2 4

OH
Acetaldehyde Cyanohydrin

(ii) Addition of Grignard reagent :

+ MgBrOH

(a) When formaldehyde is treated with Grignard reagent followed by acid hydrolysis primary
alcohol is obtained.
H H H
| | H2 O / H |
H  C  O + R–MgBr  H  C  OMgBr   H  C  OH
D
| |
R R
1 alcohol
e.g. H2O/H+
HCHO + CH3MgBr CH3 CH2 OH
Ethanol
(b) When aldehyde except formaldehyde is treated with Grignard reagent followed by hydrolysis 2°
alcohol is obtained.
O


H2 O / H
e.g. CH3–CHO + CH3MgBr  
C

OH

e.g.
H2 O / H
CH3–CHO + PHMgBr   PH CH CH3

(c) When ketone is treated with Grignard reagent followed by acid hydrolysis 3° alcohol is
obtained.

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 Organic Reaction Mechanisms-I

O C 2H 5

H O /H
e.g. CH3 C CH2 CH3 + C2H5   CH3 C C2H5
2

MgBr
OH
3-Methylpentan-3-ol

Section (D) : Bimolecular nucleophilic substitution reaction with tetrahedral

intermediate (SN2Th)
Characteristic reaction of acid and it's derivatives (acid halide, anhydride, ester and amide) is SN2Th.
Nucleophilic acyl substitution usually takes place by an addition-elimination mechanism.The incoming
nucleophile adds to the carbonyl to form a tetrasubstituted intermediate with a tetrahedral carbon.

EX
   

The tetrahedral intermediate formed, when a nucleophile attacks the carbonyl carbon of a carboxylic
acid derivative, is not stable and can not be isolated.
A pair of nonbonding electrons on the oxygen reforms the  bond, and either L or Nu is eliminated
with its bonding electrons. Whether L or Nu is eliminated depends on their relative basicities. The
weaker base is preferentially eliminated because the weaker base is the better leaving group.
D
Thus carboxylic acid derivatives will undergo a nucleophilic acyl substitution reaction provided that the
O
incoming nucleophile is a stronger base than the group that is to be replaced. If the incoming
nucleophile and the group attached to acyl group in the starting material have similar basicities, the
tetrahedral intermediate can expect either group with similar ease. A mixture of starting material and
substitution product will result.
Conditions for acyl nucleophilic substitution reactions :

(i) L must be better leaving group than Nu, i.e., basicity of Nu should be more than that of L.
C

(ii) Nu must be a strong enough nucleophilic to attack RCOL.

(iii) Carbonyl carbon must be enough electrophilic to react with Nu.

Reactivity order :  > >

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 Organic Reaction Mechanisms-I

(a) SN2Th Reaction of carboxylic acid :

(i) Formation of acid chlorides :

(ii) Fisher's Esterification :

Carboxylic acids reacts with alcohol to form esters through a condensation reaction known as
esterification.
General Reaction :

EX
+ R–OH + H2O
Specific Examples:

+ CH3CH2–OH

+ CH3–OH
Mechanism : (Acid catalysed esterification)
D
If we follow the forward reactions in this mechanism, we have the mechanism for the acid
O
catalysed esterification of an acid. If however, we follow the reverse reactions, we have the
mechanism for the acid catalysed hydrolysis of an ester.
Acid catalysed ester hydrolysis.

Which result we obtain will depend on the conditions we choose. If we want to esterify an acid,
we use an excess of the alcohol and, if possible remove the water as it is formed. If we want to
hydrolyse an ester, we use a large excess of water that is we reflux the ester with dilute
C

aqueous HCl or dilute aqueous H2SO4.

(iii) Formation of amides :

In fact amides can not be prepared from carboxylic acids and amines unless the ammonium
salt is heated strongly to dehydrate it. This is not usually a good method of preparing amides.
O O
NH3
e.g. Ph C OH  Ph C NH2
Benzoic acid Benzamide

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 Organic Reaction Mechanisms-I

(iv) Formation of acid anhydride :

O O
P2O5
e.g. CH3 COOH + HOOC CH3  CH3 C O C CH3 + H2O

(b) SN2Th Reaction of acid derivatives :

(i) Conversion of acid derivatives to other acid derivatives.
O O

EX
R C Cl + 2NH3 R C NH2 + NH4Cl
O O
R C O R' + NaNH2 R C NH2 + R' ONa
O O O O
R C O C R + R' OH R C OR' + R C OH
O
R C NH2 + NaCl No reaction

Note: An SN2Th reaction is feasible when nucleophile is more basic than the leaving group.

(ii) Hydrolysis of acid derivatives :

O O
D
R C G R C OH + GH
O O
e.g. R C O R R C O H + R–OH
O O O
e.g. R C O C R R C O H+
O
e.g. + HCl

e.g. + NH3

Note: Hydrolysis of amides and esters are not possible in neutral medium.
C

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 Organic Reaction Mechanisms-I

 Marked questions are recommended for Revision.

PART - I : SUBJECTIVE QUESTIONS

Section (A): Electrophile, Nucleophile, Nucleophilicity, Leaving group ability & Solvent
A-1. Which of the followings are electrophile ?
(a) CN– (b) H+ (c) Br+ (d) AlCl3
(e) BH3 (f) (g) NH3 (h)
A-2. Which of the followings are nucleophile ?
(a) HS– (b) BF3 (c) C2H5–OH 
(d) (CH3)3 N (e) :CH2

EX
A-3. Arrange the given species in decreasing order of their nucleophilicity :

(a) H2O (b)

A-4. Define ambident nucleophile with an example :

A-5. In nucleophilic substitution reactions the leaving ability order for the following species is (when attached
to the sp3 hybridised carbon.)
D
A-6. Label each of the following solvent as Protic or Aprotic
(a) (b) Acetonitrile (c) Acetic acid
O
O
(Tetrahydrofuran)
O
(d) (e) (f) H C NH2
(Formamide)
(DMSO)

(g) (h) Cyclohexane (i) Amonia

C

Section (B) : Types of organic reactions and reactions of acidic hydrogen

B-1. Which of the following reactions are substitution reaction ?

Ni / H2 NH3
(a) CH2=CH2   CH3–CH3 (b)  
H
  KCN
(c) CH3–I + OH  CH3 OH  I (d) CH3–CHO  
  CH3 – C –OH
H
CN

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B-2. Which of the following reaction are addition reaction ?

H
KCN
(a) CH3 – CHO  CH3 – C –OH
H
CN
HCl
(b) CH3–CH=CH2  

Alc. KOH
(c)  

CH3 OH
(d)  

B-3. Which of the following reaction is an elimination reaction ?

EX
PCl5 Zn
(a) CH3–CH2–CH2–OH   CH3–CH2–CH2–Cl (b)  CH2 = CH2 + ZnBr2

Alc. KOH CH3 OH

(c)   CH3–CH=CH2 (d)  

B-4. An organic compound which have molecular formula C4H4O3, gives 3 moles of gas on treatment with
methyl magnesium bromide. Give structure of the compound.
B-5. Predict the product of the following reactions
(a) Methylmagnesium iodide + D2O  ?
(b) Isobutylmagnesium iodide + Phenylacetylene  ?
MgBr
D
(c) + DOCH3 

Section (C) : Nucleophilic addition reactions of carbonyl compounds

C-1. Arrange the following compounds in decreasing order of reactivity for Nucleophilic addition reaction:
O
C-2. Cyclohexanone forms cyanohydrin in good yield but 2,2,6-trimethylcyclohexanone does not. Explain
why ?
C-3. Complete the following reactions.
NaCN 1. PhMgBr
(a) Ph–C–CH3 (b) CH3–CH2–CHO  
HCl 2. H O 2

O
CHO O
C

NaCN NaCN
(c) 
H SO
 (d) 
H SO

2 4 2 4

C-4. Bring about the following conversions

(i) Acetone to 2-Methylpropan-2-ol. (ii) Ethyl magnesium chloride to propan-1-ol.
C-5. What is the product of each reaction when acetophenone treated with
(a) LiAlD4 followed by H2O (b) LiAlH4 followed by D2O
(c) NaBD4 followed by EtOH (d) NaBD4 followed by EtOD

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 Organic Reaction Mechanisms-I

Section (D) : Bimolecular nucleophilic substitution reaction with tetrahedral

intermediate (SN2Th)
D-1. How many reactions given below are proceed through SN2Th mechanism ?

(a) + NaOH  (b) CH3– –NH2 + NaI 

(c) CH3– – OH + C2H5ONa (d) CH3– – OC2H5 + NaNH2

D-2. What will be the major products of the following reactions ?


H
(a) + CH3OH  (b) CH3– –OC2H5 + H2O  
D-3. Predict the products of the following reactions :

EX
(a) + 

(b) + 

(c) + CH3OH 
D
D-4. A + B, find A and B.

D-5. Write the structure of the hydroxy acid corresponding to each of the following lactones.
O

CH3 OH
O
(a) (b)
O
O O

PART - II : ONLY ONE OPTION CORRECT TYPE

Section (A): Electrophile, Nucleophile, Nucleophilicity, Leaving group ability & Solvent
A-1. Which of the following is an electrophilic reagent?
(A) H2O (B) OH– (C) NO2+ (D) None
C

A-2. Which of the following is not a nucleophile ?

(A) AICI3 (B) (CH3)2 NH (C) C2H5OH (D) H2O
A-3. Which one of the following has maximum nucleophilicity ?
(A) CH3 S (B) (C) Et3N (D)

A-4. Out of the followings best leaving group is :

(A) F– (B) Cl– (C) Br– (D) I–

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A-5. The best leaving group is :

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

A-6. Which of the following is protic solvent ?

(A) Acetone (B) Ethanol (C) DMF (D) Ether
A-7. Which of the following is aprotic solvent ?
(A) DMSO (B) NH3 (C) H2O (D) CH3COOH
Section (B) : Types of organic reactions and reactions of acidic hydrogen

EX
B-1. Which of the following reaction is an example of elimination reaction :
H2 O NaOH
(A) CH3–CH=CH2   CH3  CH  CH3 (B) CH3–CH2–Br   CH3–CH2–OH
|
OH

Alc. KOH Fe
(C) CH3  CH  CH3   CH3–CH=CH2 (D) + Br2 
|
Br
B-2. The following reaction is an example of :
RCOOH + PCl5  RCOCl
(A) Acid-base reaction (B) Substitution reaction
(C) Addition reaction (D) Elimination reaction
D
H2 O
B-3. The following reaction is an example of 

H

(A) Acid-base reaction (B) Substitution reaction

(C) Addition reaction (D) Elimination reaction
B-4. C6H5COOH + CH3MgI ?
O
(A) C6H5COOMgI (B) CH4 (C) Both A & B (D) none
B-5. (CH3)3CMgCI on reaction with D2O produces :
(A) (CH3)3CD (B) (CH3)3COD (C) (CD3)3CD (D) (CD3)3COD
B-6. A compound X (C5H12O4) upon treatment with CH3MgX gives 4 mole of methane. Identify the structure
of (X).
C

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

B-7. How many functional group produced CH4 gas by the reaction of compound (I) with CH3MgBr.

(I)
(A) 3 (B) 4 (C) 5 (D) 6

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Section (C) : Nucleophilic addition reactions of carbonyl compounds

C-1. The correct order of reactivity of following compounds with PhMgBr will be.
(C6H5)2CO, CH3–CH=O, (CH3)2C=O
(1) (2) (3)
(A) 1 > 2 > 3 (B) 2 > 3 > 1 (C) 3 > 2 > 1 (D) 1 > 3 > 2
(i) CH3 MgBr
C-2.   Product is :
(ii) H2 O

(A) (B)

(C) (D)

EX
PhMgBr H2 O
C-3. P    
P can be :
(A) CH3COOH (B) H–COOCH3 (C) CH3–COCl (D) CH3–CH=O
C-4. Butan-2-ol is obtained by using carbonyl compound and Grignard reagent as :
(i) CH3–CH2–MgBr
(A) CH3–CH=O (B)

CH3
H 3C (i) CH3–MgBr (i) CH3–CH–MgBr
(C) C=O (D) CH2=O
H 3C
D
C-5. HCN reacts with fastest rate with :
(A) Acetone (B) Ethanal (C) Benzophenone (D) Acetophenone
4 LiAlD
C-6. The product of the reaction Ph2C=O   is

H3 O
(A) Ph2CD(OH) (B) Ph2CH(OD) (C) Ph2CD(OD) (D) None
O
Section (D) : Bimolecular nucleophilic substitution reaction with tetrahedral
intermediate (SN2Th)
D-1. The relative reactivity of acyl compounds towards nucleophilic substitution are in the order of :
(A) Acid anhydride > Amide > Ester > Acyl chloride
(B) Acyl chloride > Ester > Acid anhydride > Amide
(C) Acyl chloride > Acid anhydride > Ester > Amide
(D) Ester > Acyl chloride > Amide > Acid anhydride
D-2. Consider the following compounds :
C

(i) (ii)

(iii) (iv)
The correct order of reactivity towards hydrolysis is :
(A) (i) > (ii) > (iii) > (iv) (B) (iv) > (ii) > (i) > (iii)
(C) (ii) > (iv) > (i) > (iii) (D) (ii) > (iv) > (iii) > (i)
D-3. Which of the following method is not used for the conversion of carboxylic acid into acid halide ?
(A) RCOOH + SOCl2  (B) RCOOH + PCl5 
(C) RCOOH + Cl2  (D) RCOOH + PCl3 

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D-4. Predict the major product in the following reaction :

1. CH3MgBr (excess)
C6H5CH2CO2CH3 +
2. H

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

PART - III : MATCH THE COLUMN

1. Match List I (Reaction) with List II (Product) and select the correct answer using the code given below
the lists :
List-I List-II
H2 O
(P) CH3COCH3 + CH3MgBr   (1) CH3–CH2–CH2–OH

EX
EtOH

(Q) (2)

H2 O
 
(R) (3)

H2 O
 
(S) (4)

Codes :
P Q R S P Q R S
(A) 2 4 3 1 (B) 4 2 3 1
(C) 4 2 1 3 (D) 2 4 1 3
2. Match the List-I with List-II :
D
List-I List-II
(A) I (p) Strong nucleophile
(B) CF3 SO3 (q) Strong base
(C) H2O (r) Good leaving group
(D) CH3CH2O (s) Weak base
O
 Marked questions are recommended for Revision.

PART - I : ONLY ONE OPTION CORRECT TYPE

1. Addition reactions involves
(A) Cleavage of a -bond and formation of a new -bond.
C

(B) Cleavage of two -bonds and formation of a new -bond.

(C) Cleavage of a -bond and formation of two new -bonds.
(D) None of these.
2. Which one of the following has maximum nucleophilicity ?

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

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 Organic Reaction Mechanisms-I

NaCN
3.  

In the above reaction rate is fastest, when (X) is :

O O
|| ||
(A) –OH (B)–NH2 (C)  S  O CH3 (D)  O  S  CH3
|| ||
O O

4. Correct arrangement of the following nucleophiles in the order of their nucleophilic strength is :
(A) C6H5O– < CH3O– < CH3COO– < OH– (B) CH3COO– < C6H5O– < CH3O– < OH–
– –
(C) C6H5O < CH3COO < CH3O < OH – – (D) CH3COO– < C6H5O– < OH– < CH3O–

EX
5. Which of the following reactions is not feasible ?
(A) PhSO3H + NaHCO3 (B) Ph–OH + NaNH2
(C) CH3–NH2 + NaOH 
(D) Ph–CCH + NaH
6. Give the decreasing order of nucleophilic addition reaction of the following :
(i) HCHO (ii) PhCHO
(iii) Chloral (Cl3C–CH=O) (iv) Acetophenone
(A) iii > i > ii > iv (B) iv > ii > i > iii (C) i > iii > ii > iv (D) iii > i > iv > ii
7. Number of products formed in the following reaction(s) is/are


KCN /H
 
D
(A) 1 (B) 2 (C) 3 (D) 4

8. Products

Products obtained in the above reaction is-

(A) Diastereomers (B) Enantiomers
O
(C) Meso compound (D) Optically pure one product only
9. Consider reduction of 2-butanone.

B A, B and C are respectively.

C

(A) in all cases (B) , ,

(C) in all case (D) , ,

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10. Which of the following is correct order of esterification of following acids with CH3OH :
HCOOH, CH3COOH , CH3–CH2–COOH ,

I II III IV
(A) I = II = III = IV (B) I > II > III > IV (C) I < II < III < IV (D) I > IV > III > II
11. Esterification of the acid (P) with the alcohol (Q) will gives.

(P) ; (Q) :

(R– configuration) (±)

(A) only one enantiomer (B) a mixture of diastereomer
(C) a mixture of enantiomer (D) only one fraction on fractional distillation

EX
(1) excess PhMgBr
12. 
 X , X is
(2) H2O

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

PART - II : SINGLE AND DOUBLE VALUE INTEGER TYPE

1. How many reactions given below are examples of elimination reactions ?
H2 O
 CH3  CH  CH3
D
(I) CH3–CH=CH2 
|
OH
NaOH
(II) CH3–CH2–Br   CH3–CH2–OH
Alc. KOH
(III) CH3  CH  CH3   CH3–CH=CH2
|
Br
CH3
O
EtOH / 
(IV) CH3–CH–CH–CH 3   CH3–C=CH–CH3
CH3 Cl
Br

Alc. KOH
(V)  
C

(VI)

(VII)Ph–CH2–CH–CH3 Ph–CH–CH 2–CH3

OH Cl

HI
(VIII)

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 Organic Reaction Mechanisms-I

2. Among the following X is the number of electrophiles and Y is the number of nucleophiles. Report your
answer as X Y .

(i) CH3 (ii) I (iii) NO2 (iv) CH3


(v) NH (vi) Br (vii) Cl (viii) H+
3

(ix) AlCl3 (x) CH3OH (xi) (xii) BH3

3. Which is the strongest nucleophilic site in the following species ?

EX
4. An alcohol (A), 0.22 g of this alcohol librates 56 ml of CH4 at STP on reaction with CH3MgBr. Write the
molecular weight of alcohol which satisfy these conditions.
5. How many carbonyl compounds will give secondary alcohol with molecular formula C5H12O after
reduction with LiAlH4?
6. How many compounds out of following will give secondary alcohol on treatment with Grignard reagent ?
(a) Ph–CO–CH3 (b) Ph–CHO (c) HCHO (d) CH3CH2CHO
(e) CH3CHO (f) Ph–CO–Ph (g) HCOCl (h) CH3COOC2H5
7. What is the maximum number of moles of CH3MgCl that can be consumed by one mole of phosgene ?
D
8. Find the moleculer weight of a sweet smelling compound which react with LAH to gives only ethanol.

PART - III : ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

1. Electrophiles are
(A) Electron deficent species (B) having atleast one pair of electron
(C) Electron rich species (D) Electron pair acceptor
O
2. Which of the following is/are ambident nucleophile(s) ?
(A) NO2– (B) CN (C) NaHSO3 (D) Cl
3. The correct order of leaving group ability is/are :

(A) > (B) >

(C) > (D) >

C

4. Which of the following reactions yeild benzene ?

(A) PhMgBr + CH3–Br (B) PhMgBr + H2O
(C) PhBr + H2O (D) PhMgBr + CH3–CCH
5. Which of the following liberate hydrogen gas with NaH.
(A) CH3–COOH (B)

(C) CH3–CCH (D) CH3–CH2–OH

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 Organic Reaction Mechanisms-I

HCN
6.   Product

The correct statement about product is

(A) The product is optical inactive (B) The product is meso compound
(C) The product is mixture of two enantiomer (D) Products are in two diastereomeric forms
1. MeMgBr (1 eq.)
7.  acetone as the sole organic product.


2. H3 O

which is/are correctly matched with R and R.

EX
(A) R is –H (B) R’ is (C) R’ is (D) R is –CH3

8. 2-Phenylbutan-2-ol can be prepared by :


ether H
(A) PhMgBr +    

O

(B) CH3MgBr + Ph—C—C2H5 


ether H
  

O

(C) C2H5MgBr + Ph—C—CH 3 

ether H
  


ether H
(D) CH3CH2CH2MgBr + PhCHO    

D
9. The correct decreasing reactivity order of the given compound(s) towards hydrolysis under identical
condition is/are :
(A) CH3COCl > CH3CONH2 (B) CH3COCl > (CH3CO)2O
(C) CH3COOCH3 > CH3COCl (D) (CH3CO)2O > CH3CONH2
(i) Grignard's reagent (Y) (execess)
10. X (an ethyl ester)   product
(ii)H3O
O
The product(s) may be :

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

PART - IV : COMPREHENSION
C

Read the following passage carefully and answer the questions.

Comprehension # 1
Nucleophilic aliphatic substitution reaction is given by those compounds which have electron rich
groups as leaving groups. Less is the basicity of the leaving group, more is its leaving power.
 
R – L + Nu R – Nu + L

In the given reaction, L is the leaving group which leaves as nucleophile. Nu is the incoming group
which is always nucleophilic in character. The reaction is nucleophilic substitution reaction which can be
unimolecular or bimolecular reaction.

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 Organic Reaction Mechanisms-I

1. Leaving power of which group is maximum ?


(A) ” (B) (C) (D) –Cl

2. Which one of the following is strong base but poor nucleophile ?

 
(A) CH3 (B) HO (C) (D)

Comprehension # 2

EX
Observe the following experiment

3. If the reactant ‘P’ is ethyl chloride then the main product R can be

(A) (B) CH3CH2 – O – CH2CH3

D
(C) (D)

4. If the liquid Q is H  C  OC2H5 then the product R can be (P can be any other halide)
||
O
O
(A) (B)

(C) (D)
C

5. If R is then P and Q can be respectively.

(A) , CH3– –OC2H5 (B) CH3–Cl,

(C) CH3– –CH3, (D) , CH3Cl

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 Organic Reaction Mechanisms-I

Comprehension # 3
Q.6, Q.7 and Q.8 by appropriately matching the information given in the three columns of the
following table.
Columns 1, 2 and 3 contain reactions, type of reactions and lab test for reactants respectively.
Column-1 Column-2 Column-3
H
(I) CH3–CH–CH2–CH2–C–OH 

(i) Acid base reaction (P) 2,4-DNP test
OH O
OH
Ph MgBr
(II)    (ii) Nucleophilic addition reaction (Q) Carbylamine test

O CH3
C
(iii) Nucleophilic substitution reaction (R) Lucas test

EX
NaBD 4
(III)  
H2O

CH3MgBr (iv) Fischer esterification (S) Neutral FeCl3 test

(IV) CH3–CH2–NH2   

6. For the synthesis of hydrocarbon, the only correct combination is :

(A) (II) (i) (R) (B) (III) (ii) (P) (C) (IV) (i) (Q) (D) (I) (iii) (S)

7. The only correct combination that gives two different stereoisomeric products is :
(A) (II) (i) (S) (B) (III) (iii) (P) (C) (IV) (iii) (Q) (D) (I) (iv) (R)

8. The only correct combination in which the reaction product gives iodoform test.
(A) (I) (iii) (R) (B) (III) (ii) (P) (C) (II) (i) (S) (D) (IV) (i) (Q)
D
O
C

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 Organic Reaction Mechanisms-I

EXERCISE – 1
PART – I
A-1. b, c, d, e, f, h A-2. a, c, d

A-3. (a) > > > H2O (b) > > >

EX
A-4. Ambident nucleophile: The species which have more than one nucleophilic site for reaction are called
ambident nucleophiles.
For example, cyanide ion :
–
: C  N : :C = N:¯
CH3Br + AgCN  CH3NC + AgBr
CH3Br + KCN  CH3CN + KBr
A-5. I > II > IV > III A-6. Protic solvent (c, f, i) ; Aprotic solvent (a, b, d, e, g, h)
O OH
|| |
B-1. (b), (c) B-2. (a), (b) B-3. (b), (c) B-4. HO  C  C  C  CH
|
H
D
B-5. (a) CH3 – D + (b) CH3  CH  CH3 + (c)
|
CH3

C-1. III > II > I > IV

C-2. Cyanohydrin is formed by nucleophilic attack on carbonyl group (C=O), 2,2,6-trimethylcyclohexanone
O
has more steric crowding due to three methyl groups.
CN
OH CH–OH
C-3. (a) Ph–C–CH3 (b) CH3–CH2–CH–Ph (c) (d)
CN OH
C

H2 O
C-4. (i)    +

H2 O
(ii)    CH3CH2CH2OH +

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 Organic Reaction Mechanisms-I

D H D D
C-5. (a) Ph—C—CH3 (b) Ph—C—CH3 (c) Ph—C—CH3 (d) Ph—C—CH3

OH OD OH OD
O O
|| ||
D-1. 2 (a, d) D-2. (a) CH3–C–OCH3 + HCl (b) CH3– C –OH + CH3CH2 OH

D-3. (a) (b) (c)

D-4. (A) = PhCOOH, (B) =

EX
CH3
D-5. (a) CH3–CH–CH 2–CH2–C–OH (b) CH2–CH2–C–CH2–COOH
OH O OH OH

PART - II
A-1. (C) A-2. (A) A-3. (A) A-4. (D) A-5. (A)
A-6. (B) A-7. (A) B-1. (C) B-2. (B) B-3. (C)
B-4. (C) B-5. (A) B-6. (C) B-7. (B) C-1. (B)
C-2. (A) C-3. (D) C-4. (A) C-5. (B) C-6. (A)
D-1. (C) D-2. (C) D-3. (C) D-4. (B)
D
PART - III
1. (B) 2. (A) - p, r, s ; (B) - r, s ; (C) - r, s ; (D) - p, q

EXERCISE - 2
PART - I
O
1. (C) 2. (A) 3. (D) 4. (D) 5. (C)
6. (C) 7. (B) 8. (A) 9. (B) 10. (B)
11. (B) 12. (C)
PART - II
1. 4 (III, IV, V, VI) 2. 75 3. 4 4. 88 gm. 5. 3
C

6. 4 (b, d, e, g) 7. 3 8. 88

PART - III
1. (AD) 2. (ABC) 3. (AB) 4. (BD) 5. (ABCD)
6. (AD) 7. (BD) 8. (ABC) 9. (ABD) 10. (ABC)

PART - IV
1. (B) 2. (D) 3. (C) 4. (A) 5. (B)
6. (C) 7. (D) 8. (B)

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 Organic Reaction Mechanisms-I

 Marked questions are recommended for Revision.

PART - I : PRACTICE TEST-1 (IIT-JEE (MAIN Pattern))

Max. Time : 1 Hr. Max. Marks : 120
Important Instructions
1. The test is of 1 hour duration.
2. The Test Booklet consists of 30 questions. The maximum marks are 120.
3. Each question is allotted 4 (four) marks for correct response.

EX
4. Candidates will be awarded marks as stated above in Instructions No. 3 for correct response of each
question.
¼ (one fourth) marks will be deducted for indicating incorrect response of each question. No deduction
from the total score will be made if no response is indicated for an item in the answer sheet.
5. There is only one correct response for each question. Filling up more than one response in any
question will be treated as wrong response and marks for wrong response will be deducted accordingly
as per instructions 4 above.
1. Which solvent is non-polar solvent ?
(1) CH3–CO–CH3 (2) CH3–SO–CH3 (3) CH3COOH (4) Cyclohexane
2. Which one of the following has minimum nucleophilicity ?
(1) (CH3)3CLi (2) NaNH2 (3) CH3ONa (4) NaOH
3. Which of the following compound gives fastest nucleophilic addition reaction :
D
(1) (2) (3) (4)

4. Benzoyl chloride on treatment with ammonia gives

(1) Benzamide (2) Acetamide (3) Benzylamine (4) Benzoic acid
O
5. Which of the following is a nucleophile ?
(1) CH3 (2) CH2 (3) CH3 – N (4) CH3 – NH2
6. Which of the following reactants will give only one organic product when reacted with NaCN / H 2SO4
(small amounts) (No other isomer is obtained)
O
||
(1) CH3CHO (2) HCHO (3) PhCHO (4) CH3  C  CH2  CH3
C

7. Which of the following compound give methane on treatment with CH3MgI.

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

8. The correct order of leaving ability is :

(1) > H2O (2) > (3) > (4) >

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9. In which of reaction will obtained as a product ?

(1) PhMgBr + (2) PhMgBr +

(3) PhMgBr + CH3–CH2–CH3 (4) PhMgBr +

10. Which of the following is the most reactive towards nucleophilic acyl substitution ?
O O
(1) CH3–C–NH2 (2) CH3–C–Br
O O

EX
(3) CH3–C–O–C–CH3 (4) CH3COOC2H5

O
||
NaNH2
CH3–CH2– C – OCH3 
11.  X, X is

O O
|| ||
(1) CH3–CH2– C – ONa (2) CH3–CH2– C – NH2
O
||
(3) CH3– C – NH–CH3 (4) CH3– CH2–NH2
12. Give the structure of the compound X formed in the following reaction.
D
X

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

PhMgBr + H
13.   (A) . Product (A) is :
excess
C

(1) (2)

(3) (4)

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 Organic Reaction Mechanisms-I

14. 
CH3Mg Br
 
CH3Mg Br
 
CH3Mg Br
 
H2O
 Product

(1) + (2) +

(3) (4) +

EX
15. A sweet smelling compound(x) with molecular formula C8H16O2 on reaction with excess of CH3MgBr
followed by acidification gives a single organic product(y), the structure of (y) can be :
OH OH

(1) CH3 C CH3 (2) CH3 C C2H5

CH3 C2H5
OH OH

(3) CH3 C C2H5 (4) C2H5 C C2H5

CH3 C2H5
D
16.

Give the structure of X.

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

17. Which of the following compound give benzene on reaction with PhMgBr.

1. 2. 3. 4. CH3–CCH
C

5. 6. CH3NH2 7. 8.

9. CH3SH 10.

(1) 2,3,4,5 (2) 7,8,9 (3) 2,4,5,7,10 (4) All

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 Organic Reaction Mechanisms-I

18. In which of the following reaction CH4 will be obtained.

COOH
(i) CH3–MgBr + CH3–CCH (ii) CH3 – MgBr + CH2
COOH
O
||
C – CH3
(iii) CH3–MgBr + HCN (iv) CH3 – MgBr + CH2
C – CH3
||
O
(1) (i), (ii) & (iii) (2) (i), (ii), (iii) & (iv) (3) (iii) & (iv) (4) (iii), (i) & (iv)
19. Which of the following will not give 2º alcohol ?
(1) CH3–CH2–CHO+ CH3–MgBr (2) + NaBH4

EX
CH MgBr (excess)
(3) + LiAlH4 (4) 
3
Et O


2

20. Which of these statements is incorrect about nucleophiles ?

(1) Nucleophiles have an unshared electron pair and can make use of this to react with an electron
deficient species.
(2) The nucleophilicity of an element (as electron donor) generally increases on going down a group in
the periodic table.
(3) A nucleophile is electron-deficient species
(4) All good nucleophiles are good bases when we deal across the period.
21. Which of the following reaction is substitution reaction ?
H
(1) CH3–CHO  
 CH3 – C –OH
KCN
(2) CH3–CH=CH2 
HCl

D
H
CN
(3) 
Alc. KOH
 CH3–CH=CH2 (4) 
CH3OH


22. Which of the following combination of reactants can not be used to prepare the following compound ?
O

 (1) CH3MgBr (excess) + (2) +

C

 (3) + (4) + (excess)

23. When ethyl ethanoate is treated with excess of MeMgBr followed by hydrolysis, the product is :

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

24. What product is formed when acetic acid heated with P2O5.
(1) Acetyl chloride (2) Acetate ester (3) Acetic anhydride (4) Acetaldehyde
25. Which species will not be considered as an electrophile ?
(1) CH3  CH2 (2) AlCl3 (3) NH3 (4) SO3

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 Organic Reaction Mechanisms-I

26. When grignard reagent is treated with isopropyl formate followed by acid hydrolysis we get :
(1) Aldehyde (2) 2º alcohol (3) 3º alcohol (4) 1º alcohol
27. Compound can be prepared by :

(1) (2)

(3) Ph – COCH3 (4) PhCHO

EX
28. Identify the correct set of aprotic solvent .
(1) Water, DMSO (2) DMSO, Acetone
(3) Ethanol, Acetone (4) Diethylether, Methyl amine
29. Acid hydrolysis of which of the following compounds yields two different organic compounds?
(1) CH3COOH (2) CH3CONH2 (3) CH3COOC2H5 (4) (CH3CO)2O
30. Leaving group ability order amongst the following
(I) C6H5O– (II) p-(CH3) C6H4O– (III) p-(OCH3)C6H4O– (IV) p-(NO2)C6H4O–
(1) I > II > III > IV (2) III > II > I > IV
(3) IV > I > II > III (4) IV > III > II > I

Practice Test-1 (IIT-JEE (Main Pattern))

OBJECTIVE RESPONSE SHEET (ORS)
Que. 1 2 3 4 5 6 7 8 9 10
D
Ans.

Que. 11 12 13 14 15 16 17 18 19 20

Ans.

Que. 21 22 23 24 25 26 27 28 29 30
O
Ans.

PART - II : NATIONAL STANDARD EXAMINATION IN CHEMISTRY (NSEC) STAGE-I

1. Which of the following is NOT a nucleophile ? [NSEC-2001]
(A) H2 (B) CH3OH (C) H2O (D) NH3
2. Which of the following compounds would react with PhMgBr subsequently yield Ph3COH ?
C

[NSEC-2002]
(A) a ketone (B) an ester other than formic
(C) diethyl carbonate (D) all of these.
3. Absolutely pure hydrogen cyanide fails to react with aldehydes because [NSEC-2002]
(A) hydrogen cyanide is not a strong nucleophile
(B) hydrogen cyanide is undissociated when pure
(C) hydrogen cyanide cannot add to the carbonyl group on its own
(D) all the above are correct.
4. The group which contains a Lewis acid, a nucleophile and a radical is [NSEC-2003]
(A) C2H6, Br+, CI atom (B) NH3, AICI3, H atom (C) H+, BF3, H2O+ (D) C6H6, CH3+, CI2.

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 Organic Reaction Mechanisms-I

5. The non-nucleophilic base is [NSEC-2004]

(A) CN– (B) –OC(Me)3 (C) HO– (D) MeO–
6.* The reagent with which both hexanol and 2-pentanone reacts is [NSEC-2004]
(A) Fehling`s solution (B) Grignard reagent (C) Schiffs reagent (D) Tollen`s reagent.
7. The relative reactivity of carbonyl compounds towards nucleophilic addition is [NSEC-2005]
(A) CH3CHO > CH3COCH3 > CH3COOCH3 > CH3CONH2
(B) CH3COOCH3 > CH3CONH2> CH3CHO > CH3COCH3
(C) CH3CONH2 > CH3CHO > CH3COCH3 > CH3COOCH3
(D) CH3CHO > CH3COOCH3 > CH3CONH2 > CH30OCH3.
H  OH
8. In the reactions CH3CHO + HCN  CH3CH(OH)CN   CH3CH(OH)COOH, the acid
obtained [NSEC-2006]
(A) D-isomer (B) L-isomer
(C) 80% D + 20% L mixture (D) 50% D + 50% L mixture.

EX

9. 
(i) CO2
 
(ii) H

 product

The product in this reaction will be [NSEC-2006]

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

10. The Keq values in HCN addition to following aldehydes are in the order : [NSEC-2007]
D
(A) I > II > III (B) II > III > I (C) III > I > II (D) II > I > III
11. Identify the ester which upon addition of excess Grignard’s reagent will provide a secondary alcohol :
[NSEC-2007]
(A) CH3CO2Et (B) (CH3)2CHCO2Et (C) HCO2Et (D) C6H5CO2Et
12. Which of the following series contains only nucleophiles ? [NSEC-2008]
O
(A) NH3, H2O, CN–, I– (B) AlCl3, NH3, H2O, I–
(C) AlCl3, BF3, H2O, NH3 (D) AlCl3, BF3, NO2+, NH3
13. The product/s of the following reaction is/are [NSEC-2010]

+ CH3CH2MgBr 
ether


(A) (B) + (C) + CH3CH3 (D)

C

14. The best nucleophile among the following is : [NSEC-2011]

(A) H2O (B) CH3SH (C) Cl– (D) NH3
15. A catalyst accelerates a reaction primarily by stabilizing the [NSEC-2012]
(A) substrate (B) product (C) intermediate (D) transition state
16. Which of the following information is not provided by a reaction mechanism? [NSEC-2012]
(A) Which bonds are formed and which bonds are broken
(B) Which intermediates and transition states are formed.
(C) Energy content of the reacting species
(D) Which is the slowest step
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 Organic Reaction Mechanisms-I

17. When a nucleophile attacks a carbonyl group to form an intermediate, the hybridisation of the carbon
atom changes from [NSEC-2014]
(A) sp3 to sp2 (B) sp2 to sp (C) sp to sp2 (D) sp2 to sp3
18. The product X formed in the following reaction is [NSEC-2014]
C6H5MgBr  CH3OH  X
(A) benzene (B) methoxybenzene (C) phenol (D) toluene
19. A group which departs from the substrate in a nucleophilic substitution reaction is called a leaving
group. The ease of departure is determined by the acidity of the conjugate acid of the leaving group;
higher the acidity better is the leaving group. The correct order of the reactivity of the following
compounds in a given nucleophilic reaction is : [NSEC-2016]
(A) R-Cl > R-OCOCH3 > R-OSO2CH3 > RI (B) R-OSO2CH3 > R-Cl > R-OCOCH3 > ROH
(C) R-l > RNH2 > R-OCOCH3 > R-OSO2CH3 (D) R-Br > R-OSO2CH3 > R-OCOCH3 > ROCH3
20. The correct order of the ability of the leaving group is [NSEC-2017]

EX
(A) OCOC2H5 > OC2H5 > OSO2Et > OSO2CF3 (B) OC2H5 > OCOC2H5 > OSO2CF3 > OSO2Me
(C) OSO2CF3 > OSO2Me > OCOC2H5 > OC2H5 (D) OCOC2H5 > OSO3CF3 > OC2H5 > OSO2Me
21. The best reaction sequence for the synthesis of 2-pentanone would be - [NSEC-2017]
CH3Mg /ether H ,H2O
(A) CH3CH2CH2CHO  X 


CH3Mg /ether
(B) CH3CH2CH2CN   X 
H ,H2O


CH3Mg /ether
(C) CH3CH2CH2CHO   X 
H ,H2O


(D) CH3CH2CH2Mg + CH2O 
ether
 X 
H ,H2O

22. The product 'X' in the following reaction is [NSEC-2018]
Cl
H2SO4
+ COOH X
D
OH
(A) a racemic mixture of ester (B) an optically inactive ester
(C) an optically active ester (D) a meso ester

PART - III : PRACTICE TEST-2 (IIT-JEE (ADVANCED Pattern))

Max. Time : 1 Hr. Max. Marks : 66
O
Important Instructions
A. General %
1. The test is of 1 hour duration.
2. The Test Booklet consists of 22 questions. The maximum marks are 66.
B. Question Paper Format
3. Each part consists of five sections.
4. Section 1 contains 8 multiple choice questions. Each question has four choices (A), (B), (C) and (D) out
of which ONE is correct.
C

5. Section 2 contains 6 multiple choice questions. Each question has four choices (A), (B), (C) and (D) out
of which ONE OR MORE THAN ONE are correct.
6. Section 3 contains 4 questions. The answer to each of the questions is a single-digit integer, ranging
from 0 to 9 (both inclusive).
7. Section 4 contains 1 paragraphs each describing theory, experiment and data etc. 3 questions relate to
paragraph. Each question pertaining to a partcular passage should have only one correct answer
among the four given choices (A), (B), (C) and (D).
8. Section 5 contains 1 multiple choice questions. Question has two lists (list-1 : P, Q, R and S; List-2 : 1,
2, 3 and 4). The options for the correct match are provided as (A), (B), (C) and (D) out of which ONLY
ONE is correct.

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 Organic Reaction Mechanisms-I

C. Marking Scheme %
9. For each question in Section 1, 4 and 5 you will be awarded 3 marks if you darken the bubble
corresponding to the correct answer and zero mark if no bubble is darkened. In all other cases, minus
one (–1) mark will be awarded.
10. For each question in Section 2, you will be awarded 3 marks. If you darken all the bubble(s)
corresponding to the correct answer(s) and zero mark. If no bubbles are darkened. No negative marks
will be answered for incorrect answer in this section.
11. For each question in Section 3, you will be awarded 3 marks if you darken only the bubble
corresponding to the correct answer and zero mark if no bubble is darkened. No negative marks will be
awarded for incorrect answer in this section.

SECTION-1 : (Only One Option Correct Type)

This section contains 8 multiple choice questions. Each questions has four choices (A), (B), (C)

EX
and (D) out of which Only ONE option is correct.

1. 0.34 g of hydrocarbon when treated with excess of CH3MgI liberates 112 mL of CH4 at STP the
structure of hydrocarbon is
(A) (B) CH3–CC–H

(C) CH3–CH2–CC–H (D)

2. An ester on treatment with excess of Grignard reagent followed by acidification gives Butane-2-ol and
3-methylpentan-3-ol. Predict the reactant from the following :
D
(A) + C2H5MgBr (B) + CH3MgBr

(C) + C2H5MgBr (D) +

O
3. Decreasing order of relative nucleophilicity of the following nucleophiles in protic solvent is :
, , , , H2O

(A) > > H2O > > (B) > > > > H2O

(C) > > > H2O > (D) > > > > H2O

4. Which of the following is not nucleophile ?

C

(A) OH– (B) CN– (C) BF3 (D) NH3

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 Organic Reaction Mechanisms-I

5. Which of the following will not react with acetyl chloride ?

(A) H2O (B) (C) (D)

6. Product.

In the given reaction the product is.

(A) An optically inactive mixture of two compounds

EX
(B) An optically active mixture of two compounds
(C) An optically inactive mixture of three compounds
(D) An optically active mixture of three compounds

CH3NH2 /H
7.   X, X is
heat

(A) (B)

(C) (D)
D
8. Which of the following is not correct order for Nucleophicity as well as basicity.
(A) HO >> H2O (B) NH 2 >> NH3 (C) I > Br > Cl > F (D) MeO > HO > MeCOO

Section-2 : (One or More than one options correct Type)

This section contains 6 multiple choice questions. Each questions has four choices (A), (B), (C)
and (D) out of which ONE or MORE THAN ONE are correct.
9. The correct nucleophilicity order(s) is/are:
O

(A) CH3O > CH3 (B) CH3S > CH3SH
(C) NH3 > H2O (D) (CH3CH2)3N > (CH3CH2)3P
PhMgBr HO
10. CH3  C  C  CH3 
 
2
 Fractional distillation
No of product (X)   no. of fractions (Y)
|| || (excess)
O O
X and Y are :
(A) 3 (B) 2 (C) 4 (D) 5
C

11. Which of the followings give product by SN2Th mechanism ?

(A) 
NaOH
 (B) CH3–CH2–Cl 
NaOH
 CH3–CH2–OH

(C) 
PCl5
 (D) 
PCl5

12. Choose the correct order of nucleophilicity.
       
(A) F(DMSO) > Cl(DMSO) > Br(DMSO) > I(DMSO) (B) F(aq) > Cl(aq) > Br(aq) > I(aq)
       
(C) I(aq) > Br(aq) > Cl(aq) > F(aq) (D) I(DMSO) > Br(DMSO) > Cl(DMSO) > F(DMSO)

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 Organic Reaction Mechanisms-I

13. NaSH will produce a substitution product in significant quantity with :

OMe
O O O O O Br
(A) (B) (C) (D)
Cl
C O
O
14. Which statement is/are correct for halogen
(A) Bond dissociation energy for H  X follow H  F  H  Cl  H  Br  H  
(B) Basicity order follows F   Cl   Br    
(C) Nucleophilicity order follows    Br   Cl   F 
(D) Electronegativity order follows F  Cl  Br  

Section-3 : (Single/ Double Integer Value Correct Type.)

EX
This section contains 4 questions. Each question, when worked out will result in one integer
from 0 to 9 (both inclusive)
15. A sample of 3 mg of an unknown alcohol (ROH) is added to methyl magnesium iodide then 1.12 ml gas
is evolved. What will be the molecular weight of alcohol is
16. How many types of Grignard reagent (RMgCl) can be used to prepare the following alcohol, by using
different Ketones.
Et
|
Me – C – CH(Me 2 )
|
OH
D
17. 
LiAlH4
Products
H2 O

Total number of products in the above reaction :

18. On conversion into the Grignard reagent followed by treatement with water how many structural alkyl
bromides would yield isopentane ?
SECTION-4 : Comprehension Type (Only One options correct)
This section contains 1 paragraphs, each describing theory, experiments, data etc. 3 questions
O
relate to the paragraph. Each question has only one correct answer among the four given
options (A), (B), (C) and (D)

Paragraph for Questions 19 to 21

C

19. The product P and Q are respectively :

(A) CH3OH + (CH3)2CHOH (B) (CH3)2CHOH + CH3OH
CH3
|
(C) (CH3)2CHOH + (CH3)2CHOH (D) H – C – CH3 + HO – C – CH3
|| |
O H

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 Organic Reaction Mechanisms-I

20. The product R and S are :

(A) Both 2º alcohols. (B) Both 1º alcohols.
(C) One is 1º-OH, other is 2º-OH. (D) One of these is CH3–CH2–OH.
21. One of the product of following reaction is :
(P or Q or R or S) + CH3MgBr 
(A) 3º alcohol (B) An ether (C) Methane (D) Propane

SECTION-5 : Matching List Type (Only One options correct)

This section contains 1 questions, each having two matching lists. Choices for the correct
combination of elements from List-I and List-II are given as options (A), (B), (C) and (D) out of
which one is correct
22. Match List I (Reaction) with List II (Type of reaction) and select the correct answer using the code given

EX
below the lists :
List I List II
(Reactions) (Type of mechanism)

(P) 
Br2 / h
 (1) Electrophilic addition

(Q) 
HCN / KCN
(2) Electrophilic substitution
D
(R) 
Br2 /Fe
 (3) Nucleophlic addition

(S) 
Conc.H2SO4
 (4) Free radical substitution

Codes :
O
P Q R S P Q R S
(A) 1 2 3 4 (B) 4 3 1 2
(C) 3 4 1 2 (D) 4 3 2 1

Practice Test-2 ( (IIT-JEE (ADVANCED Pattern))

OBJECTIVE RESPONSE SHEET (ORS)
Que. 1 2 3 4 5 6 7 8 9 10
C

Ans.

Que. 11 12 13 14 15 16 17 18 19 20

Ans.

Que. 21 22

Ans.

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 Organic Reaction Mechanisms-I

PART - I
1. (4) 2. (4) 3. (3) 4. (1) 5. (4)

6. (2) 7. (2) 8. (3) 9. (1) 10. (2)

11. (2) 12. (3) 13. (2) 14. (3) 15. (3)

16. (4) 17. (4) 18. (2) 19. (4) 20. (3)

21. (4) 22. (1) 23. (1) 24. (3) 25. (3)

EX
26. (2) 27. (4) 28. (2) 29. (3) 30. (3)

PART - II

1. (A) 2. (D) 3. (D) 4. (B) 5. (B)

6. (B) 7. (A) 8. (D) 9. (C) 10. (D)

11. (C) 12. (A) 13. (C) 14. (C) 15. (D)

16. (C) 17. (D) 18. (A) 19. (B) 20. (C)

21. (B) 21. (C)

D
PART - III

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

6. (B) 7. (C) 8. (C) 9. (BC) 10. (AB)

11. (AC) 12. (AC) 13. (AC) 14. (ABCD) 15. 60

O
16. 3 17. 3 18. 4 19. (C) 20. (C)

21. (C) 22. (B)

C

PART - I

2. The nucleophilicity order is > > >

4. Ph–COCl 
NH3
 Ph–CONH2 + HCl

5. The species with incomplete octet can not be a nucleophile.

6. Except HCHO all given carbonyl compound will give recemic mixture (±).

8. Weaker bases are better leaving group.

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 Organic Reaction Mechanisms-I

O O
|| ||
NaNH2 / 
11. CH3–CH2– C – OCH3   CH3–CH2– C – NH2
 CH3 ONa

12.

EX
CH3
D2O |
CH3 CH3 CH3CHCH2
| Mg | |
16. CH3CHCH2 CH3CHCH2 D
| THF | H2O
Br MgBr CH3CHCH3
(X) (Y) |
CH3

18. All of these reaction give CH4.

20. Nucleophiles are electron rich species.

O CH3
D
|| |
26. H  C  O  CH  CH3  RMgX  +
O

27. (1) (2)

C

(3) (4)

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 Organic Reaction Mechanisms-I

29. Acid hydrolysis of an ester gives two different organic compounds.

CH3COOC2H5 + H3O+  CH3COOH + C2H5OH
While the acid hydrolysis of an amide gives one organic and one inorganic product as
CH3CONH2 + H3O+  

30. Conjugated base of strong acid is weak base and behave as better leaving group.

PART - III

EX
2. Alcohols obtained from reaction of ester with Grignard reagent will have two identical alkyl group which
comes from Grignard reagent.

Therefore for & reactant should be

and CH3CH2MgBr.

3. Nucleophilicity  Size (in group)

D
7. + H2NCH3 NH–CH3
– CH3OH

9. Anionic nucleophiles are better nucleophile than their neutral species.

CH3 CH3
10. Ph OH, Ph OH &
O
Ph OH HO Ph
CH3 CH3
Methane gas is released on reacting CH3MgI with a compound containing reactive hydrogen atom. The
reaction is used for estimation of reactive hydrogen atoms present in a molecule. This method is called
zerewitinaff method of estimation of reactive hydrogen atom.

12. In aprotic solvent Nu increases, as compare to polar protic solvent.

C

O
13. HS– is better base than Cl– or –C–O– . Hence, it can substitute (A) & (C), but not (B) or (D), (D) contain
single halide which fails to undergo substitution.

14. Self understood

1.12 ml
15. Number of millimoles of alcohol =
22.4 ml / m mole

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 Organic Reaction Mechanisms-I

Wt of alcohol (mg) 3
molecular weight of alcohol = = = 60.
No. of milli moles of alcohol 1.12 / 22.4

17.

(19-21)

EX
[P, Q, R, SR–OH] + CH3MgBr  (CH4) as common product.
D
O
C

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