EXERCISE-1

Alc.KOH
Q.1   Major product is ?

(A) (B)

(C) (D)


H
Q.2  ? Product is-

R
(A) (B)

Q.3
(C)

RMgX

SI
 ? Product Obtained is-
H2O
(D)
J.
(A) (B)

(C) (D)
N.


I2 / NaOH H 
Q.4     A, A is


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


X2 OH
Q.5 (CH3)2C = C(CH3)2  A  B
H2O

(A) (B)

(C) (D) None

1
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Q.6 . In this diol

(A) OH at C2 is more basic than that of at C5

(B) OH at C2 is more acidic than at C5
(C) Both have same basicity
(D) Both have same acidic strength

( i ) CHCl3  KOH
Q.7     [X] here ‘X’ is?
( ii ) CH2 I2  NaOH

(A) (B)

R
(C) (D)

Q.8

(A)
NaNO2
  A, A is-

HCl

(B)
SI (C) (D)
J.
Q.9
N.

Select schemes A, B, C out of

I. acid catalysed hydration II. HBO III. oxymercuration-demercuration
(A) I in all cases (B) I, II, III (C) II, III, I (D) III, I, II

Q.10 Dehydration of the alcohols

(I) (II) (III) (IV)

Will be in order
(a) IV > III > II> I (B) I > II > III > IV
(C) IV > II > III> I (D) II > IV > I > III

2
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Q.11 Which one of the following can not be the product during dehydration of following
alcohol.
H




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


H3O HBr Mg / Ether HCHO HI
Q.12 CH3MgBr +   A  B    C   D 

 E, E is
H3O

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

R
Q.15 Select the odd structure out
(A) CH3 – CH (OH) – CH2 – CH3 (B) CH3–CH(OH) – CH2 – CH2 – CH3
(C) CH3 – CH (OH) – CH3 (D) CH3 – CH2 – CH (OH) – C2H5

Q.16 
 A, ‘A’ is
H3O

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

Q.17  Me3C – I + Me–OH true about this is

J.
(A) Me3C –OMe with anhydrous HI gives this reaction
(B) Me3C –OMe with concentrated HI given this reaction
(C) Both of the above
(D) None of these
N.

Q.18 The reaction of CH3OC2H5 with HI gives

(A) CH3I (B) C2H5OH
(C) CH3I + C2H5OH (D) C2H5I + CH3OH
NaBH4 H2 / Ni
Q.19 B     A, A and B are-

(A)

(B)

(C) in both cases

(D) in both cases

3
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Q.20 Consider the reaction of HI with the following:

I. II.

Which forms di-iodide on reaction with HI (excess)?

(A) I and II both (B) II Only (C) I only (D) None of these

Q.21 Ethanol on reaction with acetic anhydride gives

(A) Acetic ester (B) Formic ester
(C) Ethanoic acid (D) Acetic ester and Ethanoic acid both

Q.22 Phenol with Hinsberg’s reagent gives

(A) Sulphone (B) Sulphanilic acid (C) Sulphonic ester (D) Sulphonal

Q.23 Rate of hydration of :

R
, ,
(I) (II), (III)
Will be in order

Q.24

Q.25
(A) I < II < III

CH3OH
(A)  
CH O3
SI
(B) I < III < II

Glycol on treatment with PI3 mainly gives-

(A) Ethylene
(C) Ethyl iodide

CH3OH
 
(C) II < I < III

(B) Ethylene iodide

(D) Ethane

 (B) , A & B are:

H2SO4
(D) III < II < I
J.
(A) & (B) &
N.

(C) & (D) &

18
CH3OH H2O
Q.26 B    

 A; A and B are
CH3ONa H

(A) , (B) ,

(C) , (D) ,

4
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Q.27 How would you get racemic mixture of 1,2 butane diol from cis 2-butene.

( i) A
CH3CH = CHCH3   , A & B are
( ii )B

(A) A = KMnO4/ OH– , B = H2O (B) A = CF3CO3H, B = H2O

(C) A = OsO4/OH–, B = H2O (D) A= O3/H2O, B = Ph3P

Q.28 Which of the following reaction is called as ‘Bouveault-Blanc reduction’

(A) Reduction of acyl halide with H2PdBaSO4
(B) Reduction of ester with Na/C2H5OH
(C) Reduction of anhydride with LiAlH4
(D) Reduction of carbonyl compounds with Na/HgHCl

R
Q.29 In the following reaction, final product is
NaOC2H5
 

(A) (B)

Q.30
(C)

Cold

SI
alkaline KMnO 4
CrO3
A  
(D)

 B, A and B are
AcOH
J.
(A) (B)

(C) (D) No formation of A and B

MnO2
Q.31   A, A is
N.

(A) (B)

(C) (D)

5
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 Question No.32 to 34 (3 questions)

Q.32 Compound ‘B’ is?

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

Q.33 Organic compound A does not undergo decarboxylation reaction because?

(A) Intermediate does not follow Saytzeff'n rule
(B) Intermediate does not follow Hofmann’s rule

R
(C) Intermediate does not follow Bredt’s rule
(D) Intermediate does not follow MarkwoniKoffs rule

Q.34 Total No. of Stereoisomers of B are?

(A) 2 (B) 4 (C) 3 (D) 6

Q.35 Oxalic acid + A 

(A)
Conc.H2SO4
hence A 
SI
  B, B is:

(B) (C) (D) None

J.
EXERCISE-II

Q.1 Compound which gives alcohol on reduction is/are:

(A) (B)
N.

(C) (D)

H2O dil. H2SO4 H2

Q.2 In the reaction sequence, CaC2  A   2
 B  C,
Hg Ni

true about the product C is

(A) give yellow ppt., with NaOI
(B) its final oxidation product is carbonyl compound
(C) its final oxidation product is CO2 and H2O
(D) its final oxidation product is CH3COOH

6
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Q.3 HBO, oxymercuration-demercuration and acid catalysed hydration will not give same
product in

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

Q.4 Diethyl ether reacts with PCl5 to form

(A) Ethyl chloride
(B) Phosphorous oxy trichloride
(C) Ethenol
(D) Ethene

Q.5 Select the correct synthesis products

R

BH3 .THF H2O2 ,OH NaOH
(A)      

Hg( OAc )2 NaBH4 NaOH

(B)      
H2O

Q.6
(C)

(D)
mCPBA
 
CH2Cl2

+ (CH3)3CONa 
SI
S
N2

Lucas test is used to make distinction between 1°, 2° and 3° alcohols

anhydrous ZnCl2
ROH + HCl (conc.)     RCl  + H2O
J.
White turbidity
This shows that
(A) ROH behaves as a base
(B) greater the value of pKa (alcohol), greater the reactivity with
Conc. HCl and thus sooner the formation of white turbidity
N.

(C) alcohol which reacts fastest with Na metal, will give turbidity
at fastest rate
(D) alcohol which gives red colour during Victor Mayor test, will
give turbidity at slower rate then those giving blue or white
colour during Victor Mayor test.

Q.7 Which method is useful for the synthesis of ether?

aq.NaOH
(A) +  

(B) C2H5ONa + (CH3)2SO 4 

(C) CH3ONa + CH3CH2OSO2 

(D) (CH3)3CBr + CH3CH2ONa 

7
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Q.8 Which of the following will get oxidised by Br2/ KOH into carboxylic acid?

(A) CH3 – CH2 – OH (B)

(C) (D)

Tilden NH3 NaNO 2

Q.9 C2H5NH2   (i)  (ii)   (iii). The product (iii) can be

reagent HCl

(A) Alcohol (B) Ether

(C) Alkyl chloride (D) Alkyl nitrite
Q.10 Consider the following compound A (below)

R
Select the correct statement(s)
(A) It is more acidic than CH3OH

Q.11
(B) It is more acidic than
SI
(C) It reacts very fast with Lucas reagent
(D) It is a diacid base
Identify B and C (respectively) in following conversion.

Conc .H2SO4 OsO4 H 

   A  
 B 
 C
 H3O 
J.
(A)
&
N.

(B) &

(C) &

(D) None of these

Q.12 End product of which of following reaction give positive Iodoform test.

( i ) CH3MgBr ( excess ) ( i ) CH3MgBr ( excess )

(A)    
  (B)    
 
( ii ) H ( ii ) H

( i ) CH3MgBr ( excess ) ( i ) CH3MgBr ( excess )

(C)    
  (D)    
 
( ii ) H ( ii ) H

8
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Q.13 Predict major organic product from the following reaction:

(A) (B)

(C) (D)

R
Q.14 Which of the following reaction represent major product.

(A)

(C)
NaBH4
 

SI
LiAlH4
 
(B)

(D)
NaBH4


LiAlH4
 


J.
HI
Q.15  Products


Which of the following are possible products in the above reaction?

N.

(A) (B)

(C) I (D)

9
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Q.16 Which is/are correct statements?

CH3OH
(A)  

H2SO4

NaOH
(B)  
CH3OH

NaBH 4
(C) This is only affected in reduction to 2° alcohol  
CH3OH

R

H
(D) 

Q.17 Which can be cleaved by HIO4?

Q.18
(A)

(C)
SI (B)

(D)

Dehydration of alcohols take place more rapidly with POCl3 than with H2SO4. Select the
correct statement (s) about the following dehydration reaction
J.
POCl 2
 
Pyridine

(A) It does not involve carbocation

(B) It involves R –OPOCl2 with –OPOCl2 as a better leaving group
(C) It involves E2 mechanism as pyridine base abstracts proton from the adjacent
N.

carbon as the same time at which –OPOCl2 is leaving

(D) It is E1 reaction without formation of carbocation.
Q.19 Products form by following reactions are

CHCl3  KOH
  

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

10
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 PCC
Q.20  (X) major

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

Q.21 Methanol can be distinguished from ethanol by

(A) Heating with I2 and alkali
(B) Treating with Schiff’s reagent
(C) Treating with CrO3 solution in dil. H2SO4
(D) Treating with Lucas reagent

R
NaOH H2O
Q.22   Product is
395 C

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

Q.23 Match the column :

Column-I
(A) Identification of 1°,
2° and 3° alcohols
(B) Identification of 1°,
SI Column-II
(P) Oxymercuration demercuration

(Q) Cu/ 300° heat

2° & 3° Nitro alkanes
J.
(C) Formation of alcohol (R) Victor Mayer’s test
by anti Markovnikov’s
addition of H2O
(D) Formation of alcohol (S) Hydroboration oxidation
N.

by Markovnikov’s addition (T) Lucas test

Q.24 Match the column:
Column –I Column- II
(A) Oxidation of 1° alcohol in (P) KMnO4/
aldehyde

(B) (Q) Collin’s reagent

(C) (R) Jone’s reagent

(D) Oxidation of alkene (S) P.C.C.

into acid
11
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 Re agent R
Q.25   Alcohol

Which is true about alcohol and reagent?

Alcohol Reagent
(A) (P) B2H6, H2O 2/ NaOH

(B) (Q) PdCl2, H2O, O2/ LAH

(C) (R) Hg (OAc)2, H2O/NaBH4

R
(D) (S) dil. H2SO4

EXERCISE III

Q.1

Q.2
(iii) PhCH2CH2CH2CH3
(v) PhCH2CH2COCH3
SI
How can you convert PhCH = CHCOCH3 to
(i) PhCH = CHCO2H (ii) PhCH=CHCH2CH3
(iv) PhCH = CHCH(OH)CH3

What reagents could you use for the following conversions

(a) MeCO(CH2)2CO2Et  MeCHOH (CH2)2CO2Et
J.
(b) HO2C(CH2)4COCl  HO2C – (CH2)4CH2OH
(c) O2N (CH2)2CN  O2N (CH2)2 CH2NH2
(d) O2N (CH2)2CH = CH2  H2N (CH2)2 CH = CH2
(e) Me2CHCOCl  Me2CHCHO
(f) O2N (CH2)3 CHO  O2N (CH2)3 CH2OH
N.

(g) O2N (CH2)2 CH = CH2  O2N (CH2)3CH3

Q.3 Outline a mechanism to account for different isomer formed when reacts with

CH3OH in acidic and in basic medium.

Q.4 What are the order of rates of oxidation with HIO4 of the following diols. Explain with
reasons.
(A) Me2C(OH)C(OH) Me2 (B) Me2C(OH)CH (OH)Me
(C) CH2(OH) CH2(OH) (D) MeCH (OH) CH(OH) Me
Q.5 Differentiate:
(A) 1- Hexanol and 1-chlorohexane (B) Diethyl ether and n-butanol
(C) Diethyl ether and n-pentane

12
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Q.6 Complete the following equations and comment:
HI Na
(i) MeOEt 
 ? (ii) Et2O  ?
Q.7 Complete the following equations:
(i) n – C3H7 – CO2H  n – C4H9 OH

H
(ii) Me2CO + EtMgI  ?  ?
H2O
(iii) EtCO2Et + 2MeMgI  ?  ?
? MnO2
(iv)    ?

Q.8 t-butyl alcohol reacts less rapidly with metallic sodium than the primary alcohol. Explain
why?
Q.9 Diethyl ether behaves as base. Why?
Q.10 Sometimes explosion occurs during distillation of ether sample. Give the reason.

R
Q.11 Ethyl alcohol reacts with HI but not with HCN. Explain why?
Q.12 Write the structure of the principal organic product formed in the reaction of
1- propanol with each of the following reagents:
(i) Potassium dichromate (K2Cr2O7) in aqueous sulphuric acid, heat

(ii) Acetic acid

(iii)

(iv)
SI in the presence of dissolved hydrogen chloride.

in the presence of pyridine.

in the presence of pyridine

J.
(v) in the presence of pyridine.

Q.13 Complete the following series of equations by writing structural formula for compounds
A through I:
N.

HCl NaHCO 3 Na2Cr2O7

(a)  C5H7Cl 
  C5H8O   C5H6O
H2O H2SO4 ,H2O

Compound A Compound B Compound C

SOCl2 NaBH4
( i ) O3
(b)  C6H11Cl  C5H9ClO   C5H11ClO

pyridine ( ii ) Zn / H2O

(D) (E) (F)

NBS
(c)  Compound G
Benzoyl
peroxide ,
heat

H2O,CaCO3 PCC
   Compound H  Compound I.
Heat CH2Cl2

13
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Q.14 Predict the principal organic product of each of the following reactions. Specify
stereochemistry where appropriate.

NH3
(a)  (A)
Methanol

CH3OH
(b) + CH3ONa   (B)


HCl
(c)  (C)
CHCl3

(d) CH3(CH2)16CH2OTs + CH3CH2CH2CH2SNa  (D)

R
Q.15 Deduce the identify of the missing compounds in the following reaction sequences.
Show stereochemistry in parts (b) through (d).

(a)

(b) 
H2O
SI
( i )LiAlH4
 Compound E (C3H7ClO)
J.
KOH,H2O
  Compound F(C3H6O)

Q.16 Choose the reaction in each of the following pairs that proceeds at the faster rate.
Explain your reasoning.
N.

(a) Base- promoted hydrolysis of phenyl acetate or m- nitrophenyl acetate.

(b) Base- promoted hydrolysis of m-nitrophenyl acetate or p- nitrophenyl acetate
(c) Reaction of ethyl bromide with phenol or with the sodium salt of phenol.
(d) Reaction of ethylene oxide with the sodium salt of phenol or with the sodium
salt of p- nitrophenol
(e) Bromination of phenol or phenyl acetate.

Q.17 Explain why ArOR ethers are cleaved to give RI and ArOH rather than ArI and ROH.


PCl5 KCN H3O NH3 Heat
Q.18 C2H5OH  (A)  (B)   (C)  (D)  (E)

14
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 PBr5 KOH( Alc .) HBr NH3
Q.19 CH3CH2CH2OH  (A)   (B)   (C)  (D)

Q.20 A compound ‘X’ with molecular formula C3H8O can be oxidised to a compound 'Y’ with
the molecular formula C3H6O2, what is X?

EXERCISE –IV(A)
Q.1 The products of combustion of an aliphatic thiol (RSH) at 298 K are: [JEE 1992]
(A) CO2(), H2O (g) and SO2(g) (B) CO2(g), H2O (g) and SO2(g)

(C) CO2(), H2O () and SO2(g) (D) CO2 (g), H2O () and SO2()

Q.2 An organic compound C3H6O does not give a precipitate with 2,4- dinitrophenyl hydrazine

R
reagent and does not react with sodium metal. It could be: [JEE 1993]
(A) CH3– CH2 – CHO (B) CH3 – CO – CH3
(C) CH2 = CH – CH2OH (D) CH2 = CH – OCH3

Q.3

Q.4
(A) C6H5OH + CH3I
(C) C6H5CH3 + HOI
SI 
The reaction products of C6H5OCH3 + HI  are:
(B) C6H5I + CH3OH
(D) C6H6 + CH3OI

The order of reactivity of the following alcohols:

[JEE 1995]

[JEE 1997]
J.
(I) (II) (III) (IV)
towards conc. HCl is
(A) I > II > III > IV (B) I > III > II > IV
(C) IV > III > II > I (D) IV > II > III > I
N.

Q.5 Among the following compounds, the strongest acid is: [JEE 1998]
(A) HC  CH (B) C6H6 (C) C2H6 (D) CH3OH
Q.6 Which one of the following will most readily be dehydrated in acidic condition:
[JEE 2000]

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

Q.7 Identify the correct order of boiling point of the following compounds: [JEE 2002]
CH3CH2CH2CH2OH CH3CH2CH2CHO CH3CH2CH2COOH
1. 2. 3.
(A) 1 > 2 > 3 (B) 3 > 1 > 2 (C) 1 > 3 > 2 (D) 3 > 2 > 1

15
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 – 
C2H5O Na ( excess )
Q.8 + C2H5I     [JEE 2003]
C2H5OH ( anhydrous )

(A) (B)

(C) C6H5OC6H5 (D) C2H5OC2H5

Q.9 Reaction of entainomerically pure acid with 1 chiral carbon and racemic alcohol with 1 chiral
carbon gives an ester which is [JEE 2003]
(A) Meso (B) Optically active mixture
(C) Racemic mixture (D) Enantionmerically pure
Q.10 On acid catalysed hydration, 2- phenyl propene gives: [JEE 2004]

R
(A) 3- phenyl-2- propanol (B) 2-phenyl-1- propanol
(C) 1- phenyl-3- propanol (D) 2- phenyl -2- propanol

Q.11 Phenyl magnesium bromide reacting with t- Butyl alcohol gives: [JEE 2005]

Q.12
(A) Ph – OH

(C) SI (B) Ph – H

(D)

Statement-1: p- Hydroxybenzoic acid has a lower boiling point than o-hydroxybenzoic acid.
[JEE 2007]
Because
J.
Statement-2: o- Hydroxybenzoic acid has intramolecular hydrogen bonding.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-1 is True, Statement-2 is True, Statement-2 is NOT a correct explanation for
Statement-1.
N.

(C) Statement-1 is True, Statement-2 is False.

(D) Statement-1 is False, Statement-2 is True.

16
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 EXERCISE –IV(B)
Q.1 When t-butanol and n- butanol are separately treated with a few drops of dilute KMnO4 in one
case only, purple colour disappears and a brown precipitate is formed. Which of the two
alcohols gives the above reaction and what is the brown precipitate? [JEE 1994]

Q.2 3,3-Dimethylbutan-2-ol losses a molecule of water in the presence of a concentrated sulphuric

acid to give tetramethyl ethylene as a major product. Suggest a suitable mechanism.
[JEE 1996]

Q.3 A compound D(C8H10O) upon treatment with alkaline solution of iodine gives a yellow
precipitate. The filtrate on acidification gives a white solid (E) (C7H6O2). Write the structures of
(D) and (E) and explain the formation of (E). [JEE 1996]

R
Q.4 Which of the following is the correct method for synthesising methyl-t-butyl ether and why ?
(i) (CH3)3CBr + NaOMe 
(ii) CH3Br + tert-BuOna  [JEE 1997]

Q.5

Q.6
+ SI
Conc .H SO
   4  (A)
2 

Discuss why o-hydroxy benzaldehyde is a liquid at room temperature while

p- hydroxy benzaldehyde is a high melting solid?
[JEE 1997]

[JEE 1999]
J.
Q.7 Write the structures of the product A and B. [JEE 2000]

H3O
  A + B

Q.8 Cyclobutyl bromide on treatment with magnesium in dry ether forms an organometallic
N.

A. The organometallic reacts with ethanol to give an alcohol B after mild acidification.
Prolonged treatment of alcohol B with an equivalent amount of HBr gives 1- bromo-1-
methylcyclopentane (C). Write the structures of A, B and explain how C is obtained
from B. [JEE 2001]
Q.9 Identify X, Y and Z in the following synthetic scheme and write their structure. Explain
the formation of labelled formaldehyde (H2C*O) as one of the products when compound
Z is treated with HBr and subsequently ozonolysed. Mark the C* carbon in the entire
scheme. [JEE 2001]
BaC*O3  H2SO4  X (gas) [C* denotes C14]
( i )Mg / ether LiAlH4
CH2 = CH – Br    
Y   Z
( ii ) X, ( iii )H3O

17
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Q.10 Mention two esters produced when a racemic mixture of 2- phenyl propanoic acid is
treated with (+) 2- butanol. What is the stereochemical relationship between these
esters? [JEE 2003]

Q.11 An organic compound P(C5H10O) Reacts 1015 times faster then ethylene with dil. H2SO4
to give two products Q and R. Both Q and R give positive iodoform test. Identify P, Q
and R and also give reason for very high reactivity of P. [JEE 2004]

NaNO 2 , HCl
Q.12 (X) C5H13N    (Y) (Tertiary alcohol + other products)
N2

(Optically active)
Find X and Y. Is y optically active? Write the intermediate steps. [JEE 2005]

R
SI
J.
N.

18
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 ANSWER KEY

EXERCISE-1
Q.No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. D D B A A A C D C C C D A D D
Q.No. 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Ans. B C C B C D C C A B A B B D A
Q.No. 31 32 33 34 35
Ans. A C C A A

EXERCISE-2

Q.No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. A,C,D A,C A,B,D A,B A,B,C A,B,D A,B,C A,B A,B,C,D A,B, C A,B,C,D B A,C B,C,D
Q.No. 16 17 18 19 20 21 22 A B C D
23

R
Ans. A,B,C,D B A,B,C A,C C A A,B Q,R,T R S P
Q.No. A B C D A B C D
24 25
Ans. Q,R,S S Q P P R S Q

EXERCISE-3

Q.1
Q.2

Q.3

Q.4
Q.5
(i) I2 + NaOH (ii) NaH4 + OH
(a) NaBH4

In acidic medium
(b) NaBH4
(e) H2 – Pd/ BaSO4

a < b < d < c (steric factor)

SI
and
(iii) ZnHgHCl (iv) not LiAlH4
(c) Na + C2H5OH
(f) NaBH4

In basic medium

3+
(v) N2H2
(d) LiAlH4
(g) N2/ H2

(a) 1- hexanol reduces organ red CrO3 to green Cr ; while 1- chlorohexane gives white ppt. of AgCl on
warming with ethanolic AgNO3
J.
(b) n-Butanol gives a positive test with CrO3 in acid and evolves H2 with sodium; while dry ethyl etheris
negative to both tests.
(c) Unlike n-pentane, diethyl ether is basic and dissolves in conc. H2SO4
+ –
(C2H5)2O + H2SO4  (C2H5)2 OH + HSO4
Q.6 (i) MeI + EtOH due to SN2 mechanism
(ii) No reaction

LiAlH H
Q.7 (i) n-C3H7CO2H 
4
 n – C4H9OH (ii) Me2CO + EtMgI   Me2C(OH)Et
N.

or B2H6

H2O
(iii) EtCO2Et + 2MeMgI   EtCMe2OH

LiAlH4
 
(iv)

MnO2
 

19
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Q.8 The + I.E. of three methyl groups on central C-atom of tert- butyl alcohol makes is partially negative with the
result that it pushes the electron pair of –OH bond towards H-atom and thus H- atom is not replaced easily.

(less partial +ve charge) (more partial +ve charge)

Q.9 Oxygen atom is diethyl ether molecule has two lone pair of electrons available for coordination. Therefore
ethers behaves as Lewis base forming oxonium salts.

+ –
+ HCl  R2OH Cl (dialkyl oxonium chloride)

Q.10 Due to the formation of explosive peroxide by oxidation.

Q.11 Ethanol being very weak Lewis base and thus reacts with stronger acid HI.

R
Q.12 (i) CH3CH2COOH (ii) CH3COOCH2CH2CH3
(iii) MePhSO2OCH2CH2CH3 (iv) PhCOOH + PhCOOCH2CH2CH3

(v)

Q.13 (A)

(D) CH2 = CH – CH2(Cl) – CH3

SI (B)

(E) CH3CH(Cl)CH2CH2CHO
(C)

(F) CH3 – CH (Cl) CH2CH2CH2OH

(G) (H) (I)

J.
Q.14 (a) (b)
N.

(c) Ph – CH(Cl) – CH2OH (d) H3C – CH2 – CH2 – CH2 – S – CH2 – (CH2)16 – CH3

Q.15 (A) CH2 = CH – CH2 – CH2OH (B) Br = CH2CH (Br) CH2CH2OH

(C) (D) (E) (F)

Q.16 (a) m-nitrophenyl acetate (better leaving group) (b) p-nitrophenyl acetate (better leaving group)
(c) sodium salt of phenol (better nucleophile) (d) sodium salt of phenol (better nucleophile)
(e) Phenol (more activated aromatic ring)

Q.17 SN2 attack on a carbon of a benzene ring does not occur nor does the high energy C6H5+ form by an SN1
reaction. Hence ArI cannot be a product even in an excess of conc. HI.
Q.18 (A) C2H5Cl ; (B) C2H5CN ; (C) C2H5COOH; (D) C2H5COONH4 (E) C2H5COH2
Q.19 (A) C3H7Br; (B) CH3CH = CH2 (C) CH3CHBrCH3 (D) CH3CHNH2CH3
Q.20 CH3CH2CH2OH

20
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 EXERCISE-4 (A)

Q.1 B Q.2 D Q.3 A Q.4 C Q.5 D Q.6 A

Q.7 B Q.8 D Q.9 B Q.10 D Q.11 B Q.12 D

EXERCISE-4 (B)

Q.1 n- butanol is oxidised by KMnO4 and not t- butanol as the latter does not contain H atom attached to carbinol
carbon atom.
– 
CH3CH2CH2CH2OH + KMnO4  CH3CH2CH2COO OK + MnO2 + KOH
n- Butanol Brown

+ KMnO4  No reaction

t- Butanol

R
H H O
Q.2 
 2
 

1, 2  methyl shift – H

Q.3

Q.4
    

(D)
SI  

(E) C6H5COOH

The ether formation involves nucleophilic substitution of alkoxide ion for halide ion.
Slow
 
Fast
 R – O – R + X
–

3° alkyl halide can also involve elimination of HX to give alkene in the presence of a base. So, it is better to
start with 3° alkoxide and 1° alkyl halide, i.e., equation (b).
J.
Q.5 Q.6 Due to intermolecular H-Bonding. Q.7

Mg MeCHO H O HBr
Q.8 
    3
 
N.

Et 2O

(A) (B) (C)

Mechanism

H H O
2

   

Br 
 

2°carbonium 3° carbonium

Q.9 ;

21
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Q.10 +

(recemic mixture)

during esterification reaction only –COOH and – OH participates. There is no effect on structure of
configuration of carbon adjacent of these groups. So when (±) acid reacts with pure (+) alcohol two esters are
produced which are diastereoisomers of each other.

Q.11

R
Q : CH3CH2OH

When ethylene reacts with dil. H2SO4CH3CH2  is produced during rate determining step, whereas P gives

Q.12
SI
resonance stabilized intermediate.

due to extra stability of intermediate the rate of reaction is very fast.

J.
Y is optically inactive.
N.

22
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