ALCOHOLS

&
ETHERS
 EXERCISE-I

Q.1 Alc
. KOH
 Major product is

(A) (B)

(C) (D)


Q.2 H ? Product is:

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

Q.3 RMgX
  ? Product Obtained is:
H 2O

R R'
| |
(A) R 'C  CH 2OH (B) RCH 2  C  OH
| |
R'' R' '

R R
| |
(C) R ' CH 2  C  OH (D) R ' ' CH 2  C  OH
| |
R'' R'

I / NaOH
Q.4 
2
 H
 
 A, A is


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

Alcohols & Ethers [2]

 X 
Q.5 (CH3)2C = C(CH3)2 
2
A OH
 B
H 2O

(A) (B) (CH 3 ) 2 C  C(CH 3 ) 2

| |
OH Cl

(C) (CH 3 ) 2 C  C(CH 3 ) 2 (D) None

| |
OH OH

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 ) CHCl  KOH
Q.7   
3
 [X] here ‘X’ is:
(ii ) CH 2I 2  NaOH

(A) (B)

(C) (D)

NaNO
Q.8  
2  A
HCl

A is

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

Q.9

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

Alcohols & Ethers [3]

Q.10 Dehydration of the alcohols

will be in order
(A) IV > III > II > I (B) I > II > III > IV (C) IV > II > III > I (D) II > IV > I > III

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

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

H O
HBr HCHO
Q.12 CH3MgBr + 
3
 A  B Mg
 /
ether
 C    D 
HI E
H O 3

E is

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

LiAlH
Q.13 Glycerol KHSO
 4  A  
4  B

A and B are:
(A) Acrolein, allyl alcohol (B) Glyceryl sulphate, acrylic acid
(C) Allyl alcohol, acrolein (D) Only acrolein (B is not formed)

Q.14 3-methyl-3-hexanol can not be prepared by

(A) CH3MgI and 3-hexanone, followed by hydrolysis
(B) C2H5MgI and 2-pentanone, followed by hydrolysis
(C) C3H7MgI and 2-butananone, followed by hydrolysis
(D) C4H9MgI and propanone, followed by hydrolysis

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

Alcohols & Ethers [4]

Q.16 
  A. ‘A’ is
H 3O

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

CH 3
 |
Q.17 CH 3  O  C  CH 3  Me3C–I + Me–OH true about this is
| |
H CH 3
(A) Me3C–OMe with anhydrous HI gives this reaction
(B) Me3C–OMe with concentrated HI gives this reaction
(C) both of the above
(D) none

Q.18 The reaction of CH3OC2H5 with HI gives

(A) CH3I (B) C2H5OH (C) CH3I + C2H5OH (D) C2H5I + CH3OH

NaBH H / Ni
Q.19 B  
4 CH = CH – CHO 2  A
A and B are:

(A) CH2CH2CHO, CH = CH–CH2OH

(B) CH2CH2CH2OH, CH = CH – CH2OH

(C) CH= CH–CH2OH in both cases

(D) CH2CH2CH2OH in both cases

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

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

Alcohols & Ethers [5]

Q.22 Phenol with Hinsberg’s reagent gives
(A) Sulphone (B) Sulphanilic acid (C) Sulphonic ester (D) Sulphonal

Q.23 Rate of hydration of

, ,

will be in order:
(A) I < II < III (B) I < III < II (C) II < I < III (D) III < II < I
Q.24 Glycol on heating with PI3 mainly gives–
(A) Ethylene (B) Ethylene iodide (C) Ethyl iodide (D) Ethane

CH OH
Q.25 (A)  
3CH OH
 3
 (B) A & B are:
H 2SO 4
CH 3O 

(A) & (B) &

(C) & (D) &

CH OH H O18
Q.26 B  
3
 2  A
CH 3ONa H

A and B are

CH 3 CH 3 CH 3 CH 3
| | | |
(A) CH 3  C  CH 2 , CH 3  C  CH 2 (B) CH 3  C — CH 2 , CH 3  C  CH 2
| | | | | | | |
OH OH OH OCH 3 OH18OH OH OCH 3
18

CH 3 CH 3 CH 3 CH 3
| | | |
(C) CH 3  C  CH 2 , CH 3  C — CH 2 (D) CH 3  C — CH 2 , CH  C — CH
3 2
| | | | | | | |
OH OH 18
OH OH 18 OCH 3 OH
18 18 18OH OH

Alcohols & Ethers [6]

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

OH
(i ) A
|
CH3CH = CHCH3  CH 3  CH  CH  CH 3 , A & B are
( ii ) B
|
(A) A = KMnO4/OH– , B = H2O OH (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

Q.29 In the following reaction, final product is

14
ClCH 2 CH  C H 2 NaOC H
 25 
\ /
O
14 14
(A) ClCH 2CH C H 2OC 2 H 5 (B) ClCH 2CH C H 2ONa
| |
OH OC 2 H 5

14 14
(C) C H 2  CHCH 2 OC 2 H 5 (D) CH 2  CH C H 2OC 2 H 5
\ / \ /
O O
cold
Q.30    A CrO
3  B
alkaline KMnO4 AcOH

A and B are:

(A) , (B) ,

(C) , (D) no formation of A and B

MnO
Q.31 CH 2  CHCHCH 2 CH 2OH 2  A. A is

|
OH

(A) CH 2  CHCCH 2 CH 2OH (B) CH 2  CHCHCH 2CHO

|| |
O OH

O
||
(C) CH 2  CHCCH 2CHO (D) CH 2  CHCCH 2COH
|| ||
O O
Alcohols & Ethers [7]
 Question No 32 to 34 (3 questions)

Q.32 Compound 'B' is?

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

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

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

hence A conc . H SO
 24  B, B is:
O
O
(A) (B) (C) CH 2  O  CH 2 (D)
O
| | O
OH OH

Alcohols & Ethers [8]

 EXERCISE-II

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

|| ||
(A) Me  C  Cl (B) Me  C  NH 2 (C) Me  CH  CH 2 (D) Me  C  OC  Me
|| || \ /
O O O

dil. H 2SO 4 H
Q.2 In the reaction sequence, CaC2 H
2O
 A    B 
2
C, true about the product C is
2 Ni
Hg
(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

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

BH ·THF H O , OH
(A) 3 2 
2
 NaOH
 

Hg ( OAc) NaBH
(B)    4  NaOH
2    
H 2O

(C) mCPBA
 
CH 2Cl2

(D)

Q.6 Lucas test is used to make distinction between 1°, 2° and 3° alcohols
ROH + HCl anhydrous ZnCl
   2  RCl  + H2O
conc.
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.
(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.

Alcohols & Ethers [9]

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

(A) aq
. NaOH

(B) C2H5ONa + (CH3)2SO4 

(C) CH3ONa + CH3CH2OSO2 

(D) (CH3)3CBr + CH3CH2ONa 

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

(A) CH3–CH2–OH (B) CH  CH 3

|
OH

(C) CH2OH (D)

Tilden NH 3 NaNO2
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)

O
Select the correct statement(s) ||
(A) It is more acidic than CH3OH (B) It is more acidic than CH 3COH
(C) It reacts very fast with Lucas reagent (D) It is a diacid base

Q.11 Identify B and C (respectively) in following conversion.


conc
 .H 2SO 4
 A OsO
4  B H
 C
  
H 3O

OH
(A) &
OH
OH OH
(B) &

O
OH
(C) &
OH
(D) None of these

Alcohols & Ethers [10]

Q.12 End-product of which of following reaction give positive Iodoform test.
O O
|| (i ) CH MgBr ( excess ) || (i ) CH MgBr ( excess )
(A) H  C  Cl  3   
  (B) Ph  C  O  Et  3   
 
(ii ) H (ii ) H

O O
|| || (i ) CH MgBr ( excess )
(C) H  C  O  Et (
i ) CH 3MgBr ( excess )
     (D) CH 3  C  H  3   
 
(ii ) H  (ii ) H

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

(A) (B)

(C) (D)

Q.14 Which of following reaction represent major product.

(A) NaBH
4  (B) NaBH
4 

(C) LiAlH
4  (D) LiAlH
4 

Alcohols & Ethers [11]

 HO

Q.15 HI
Products

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

I
I

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

I

Q.16 Which is/are correct statements?

(A)

(B)

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

(D)

Q.17 W hich can be cleaved by HIO4?

O O OH O
|| || | ||
(A) CH CH CCH CCH (B) CH 3CHCCH 2 CH 3
3 2 2 3

O O
|| ||
(C) (D) CH 3CCH 2 CHCH 2CCH 3
|
OH

Alcohols & Ethers [12]

Q.18 Dehydration of alcohols take place more rapidly with POCl3 than with H2SO4. Select the correct
statement(s) about the following dehydration reaction.
POCl
3 
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 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

CHCl KOH
 3 

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

OH

Q.20  (X) Major

PCC

CH3 OH

OH O O OH

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

O O OH

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

NaOH H O
Q.22   
2
 Product is:
395C

(A) (B)

(C) (D)

Alcohols & Ethers [13]

Q.23 Match the column:
Column I Column II
(A) Identification of 1°, 2°& 3° Alcohols (P) Oxymercuration demercuration
(B) Identification of 1°, 2°& 3° Nitro alkanes (Q) Cu/300° heat
(C) Formation of alcohol by anti Markovnikov's (R) Victor Mayer's test
addition of H2O
(D) Formation of alcohol by Markovnikov's (S) Hydroboration oxidation
addition
(T) Lucas test

Q.24 Match the column:

Column I Column II
(A) Oxidation of 1°alcohol in aldehyde (P) K M nO 4/

(B) CrO3 . .HCl (Q) Collin's reagent

(C) CrO3 .2 (R) Jone's reagent

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

Q.25 CH 3  CH  CH  CH 2 Re
agent
 R
 Alcohol
|
CH 3
which is true about alcohol and Reagent ?
Alcohol Reagent
(A) CH 3  CH  CH 2  CH 2OH (P) B2H6 , H2O2 / NaOH
|
CH 3

CH 3  CH  CH  CH 3
(B) | | (Q) PdCl2, H2O, O2 / LAH
CH 3 OH
OH
|
(C) CH 3  C  CH 2CH 3 (R) Hg(OAc)2, H2O / NaBH4
|
CH 3
(S) dil. H2SO4

Alcohols & Ethers [14]

 EXERCISE-III

Q.1 How can you convert PhCH = CH COCH3 to

(i) PhCH = CHCO2H (ii) PhCH = CHCH2CH3 (iii) PhCH2CH2CH2CH3
(iv) PhCH = CHCH(OH)CH3 (v) PhCH2CH2COCH3

Q.2 What reagents could you use for the following conversions
(a) MeCO(CH2)2CO2Et  MeCHOH(CH2)2CO2Et
(b) HO2C(CH2)4 COCl  HO2C –(CH2)4CH2OH
(c) O2N(CH2)2CN  O2N(CH2)2 CH2NH2
(d) O2N(CH2)2 CH = CH2  H2N(CH2)2CH=CH2
(e) Me2CHCOCl  Me2CHCHO
(f) O2N(CH2)3CHO  O2N(CH2)3 CH2OH
(g) O2N(CH2)2CH=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) Me CH(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

Q.6 Complete the following equations & comment:

HI
(i) MeOEt  ? Na
(ii) Et2O  ?

Q.7 Complete the following equations:

(i) n – C3H7 – CO2H  n – C4H9OH

(ii) Me2CO + EtMgI  ? H ?
H O
(iii) EtCO2Et + 2MeMgI  ? 
2
?
? MnO
(iv) CHCO2Et 
 CHCH2OH 2  ?

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.

Q.11 Ethyl alcohol reacts with HI but not with HCN. Explain why?

Alcohols & Ethers [15]

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 sulfuric acid, heat
O
||
(ii) Acetic acid CH 3COH in the presence of dissolved hydrogen chloride.

(iii) CH3 SO2Cl in the presence of pyridine

O O
|| ||
(iv) C6 H 5COCC6 H 5 in the presence of pyridine

(v) in the presence of pyridine

Q.13 Complete the following series of equations by writing structural formula for compounds A through I:
NaHCO Na Cr O
(a)  C5H7Cl H
HCl
 O
3  C5H8O 227  C5H6O
H SO , H O
2 2 4 2
Compound A Compound B Compound C
SOCl (i ) O NaBH
(b) CH2 = CHCH 2 CH 2CHCH 3 2  C6H11Cl   3
 C5H9ClO  
4  C5H11ClO
pyridine ( ii ) Zn / H 2O
|
OH (D) (E) (F)

H O ,CaCO
(c) NBS
 Compound G 2  3  Compound H PCC
 Compound I
benzoyl heat CH 2Cl 2
peroxide ,
heat

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

NH
(a) 
3  (A)
methanol

CH OH
(b) + CH3ONa 3
 (B)

(c) HCl
 (C)
CHCl3

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

Alcohols & Ethers [16]

Q.15 Deduce the identify of the missing compounds in the following reaction sequences. Show stereochemistry
in parts (b) through (d).
( i ) Mg Br2
(a) CH 2 = CHCH2Br  compound A(C4H8O) 
 compound B(C4H8Br2O)
( ii ) CH 2 O
( iii ) H3O 

KOH
compound D  compound C (C4H7BrO)
Heat

( i ) LiAlH
(b)   4  compound E (C3H7ClO) KOH

, H 2O
 compound F (C3H6O)
H 2O

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

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

PCl 
Q.18 C2H5OH 5  (A) KCN
 (B) H
3O
NH 3
 (C)  (D) heat
 (E)

HBr
Q.19 CH3CH2CH2OH PBr

KOH ( Alc.)
5  (A)     (B)  (C) NH
3  (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' ?

Alcohols & Ethers [17]

 EXERCISE-IV (A)

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

Q.2 An organic compound C3H6O does not give a precipitate with 2,4-dinitrophenyl hydrazine 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 
The reaction products of C6H5OCH3 + HI  are: [JEE 1995]
(A) C6H5OH + CH3I (B) C6H5I + CH3OH
(C) C6H5CH3 + HOI (D) C6H6 + CH3OI

Q.4 The order of reactivity of the following alcohols: [JEE 1997]

towards conc. HCl is:

(A) I > II > III > IV (B) I > III > II > IV (C) IV > III > II > I (D) IV > II > III > I

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

C H O  Na  ( excess)
Q.8 OH + C2H5I      
2 5 [JEE 2003]
C 2H5OH ( anhydrous)

(A) OC2H5 (B) I (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

Alcohols & Ethers [18]

Q.10 On acid catalysed hydration, 2-phenyl propene gives: [JEE 2004]
(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]

(A) Ph – OH (B) Ph – H (C) (D)

Q.12 Statement-1: p-Hydroxybenzoic acid has a lower boiling point than o-hydroxybenzoic acid.[JEE 2007]
because
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.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

Alcohols & Ethers [19]

 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]
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]

O  C  OH HOCH2
Conc.H 2SO 4
Q.5 | + |     (A) [JEE 1997]
O  C  OH HOCH2

Q.6 Discuss why o-hydroxy benzaldehyde is a liquid at room temperature while p-hydroxy benzaldehyde is
a high melting solid? [JEE 1999]
Q.7 White the structures of the product A & B [JEE 2000]

CH 3  C  O18C 2 H 5 H
3O
 A + B
||
O

Q.8 Cyclobutyl bromide on treatment with magnesium in dry ether forms an organometallic A. The
organometallic reacts with ethanal 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 C ]
* * 14

(i ) Mg / ether LiAlH 4
CH2 = CH – Br    
Y    Z
( ii ) X ,( iii ) H 3O

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]

Q.12 (X) C5H13N NaNO ,HCl

 2 (Y) (Tertiary alcohol + other products)
 N2

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

Alcohols & Ethers [20]

 ANSWER KEY
EXERCISE-I
Q.1 D Q.2 D Q.3 B Q.4 A Q.5 A Q.6 A Q.7 C
Q.8 D Q.9 C Q.10 C Q.11 C Q.12 D Q.13 A Q.14 D
Q.15 D Q.16 B Q.17 C Q.18 C Q.19 B Q.20 C Q.21 D
Q.22 C Q.23 C Q.24 A Q.25 B Q.26 A Q.27 B Q.28 B
Q.29 D Q.30 A Q.31 A Q.32 C Q.33 C Q.34 A Q.35 A
EXERCISE-II
Q.1 A,C,D Q.2 A,C Q.3 A,B,D Q.4 A,B
Q.5 A,B,C Q.6 A,B,D Q.7 A,B,C Q.8 A,B
Q.9 A,B,C,D Q.10 A,B Q.11 C Q.12 A,B,C,D
Q.13 B Q.14 A,C Q.15 B,C,D Q.16 A,B,C,D
Q.17 B Q.18 A,B,C Q.19 A,C Q.20 C
Q.21 A Q.22 A,B Q.23 (A) Q,R,T, (B) R, (C) S, (D) P
Q.24 (A) Q,R,S (B) S (C) Q (D) P Q.25 (A) P; (B) Q, R; (C) S
EXERCISE-III
Q.1 (i) I2 + NaOH (ii) N2H4 + OHr (iii) ZnHgHCl (iv) not LiAlH4 (v) N2H2
Q.2 (a) NaBH4 (b) NaBH4 (c) Na + C2H5OH (d) LiAlH4
(e) H2 – Pd / BaSO4 (f) NaBH4 (g) N2H4 + OHr
OCH 3 OCH 3
| |
Q.3 In acidic medium Me 2  C  CH 2 and In basic medium Me 2 C  CH 2
| |
OH O
Q.4 a < b < d < c (steric factor)
Q.5 (a) 1-hexanol reduces organ red CrO3 to green Cr3+; while 1-chlorohexane gives white ppt. of AgCl on
warming with ethanolic AgNO3.
(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)2OH+ + HSO 4
Q.6 (i) MeI + EtOH due to SN2 mechanism (ii) No reaction
Q.7 (i) n – C3H7CO2H LiAlH
 4  n – C4H9OH
or B2H 6


(ii) Me2CO + EtMgI  M2C H Me2C(OH)Et

(iii) EtCO2Et + 2MeMgI  H 2O

 EtCMe2OH

LiAlH MnO
(iv) CHCO2Et  
4  CHCH2OH 2  CHCHO

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)

Alcohols & Ethers [21]
Q.9 Oxygen atom in diethyl ether molecule has two lone pair of electrons available for co-ordination. Therefore
ethers behave as Lewis base forming oxonium salts.

O: + 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
Q.12 (i) CH3CH2COOH (ii) CH3COOCH2CH2CH3 (iii) MePhSO2OCH2CH2CH3

(iv) PhCOOH + PhCOOCH2CH2CH3 (v)

Q.13 (A) (B) (C)

(D) CH2 = CH–CH2 – CH2 – CH (Cl) – CH3 (E) CH3CH(Cl)CH2CH2CHO

(F) CH3–CH(Cl) CH2CH2CH2OH (G)

(H) (I)

OMe
Q.14 (a) (b) CH2Ph (c) Ph–CH(Cl)–CH2OH
OH
(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) C2H5CONH2
Q.19 (A) C3H7Br; (B) CH3CH=CH2 (C) CH3CHBrCH3 (D) CH3CHNH2CH3
Q.20 CH3CH2CH2OH
EXERCISE-IV (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

Alcohols & Ethers [22]

 EXERCISE-IV (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  CH 3CH 2CH 2 COO O K + MnO2 + KOH
n-Butanol Brown
CH 3
|
CH 3  C  CH 3 + KMnO4  No reaction
|
OH
t-Butanol
H Me H Me Me
| |  | |  |
Q.2 CH 3  C — C  CH 3 H CH 3  C — C  CH 3 
H 2O
 CH 3  C H  C  CH 3
| | | | |
O H  Me
  Me 
H O H Me


Me Me
|  |
H
CH 3  C  C  CH 3  CH 3  CH  C CH 3
| 
|
Me Me

Q.3 (D) Ph  CH  CH 3 (E) C6H5COOH

|
OH
Q.4 The ether formation involves nucleophilic substitution of alkoxide ion for halide ion.
 
Fast
Slow
 R ' O ------ R ------ X  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)

Q.5 Q.6 Due to intermolecular H-Bonding

Q.7 A  CH 3  C  OH , B = C2H5O18H
||
O

H O
Q.8 Mg
 MeCHO
  
3
 HBr

Et 2O
(A) (B) (C)

Alcohols & Ethers [23]

 Mechanism


H 
2 H O
 


 Br

2°carbonium 3° carbonium

* * * *
Q.9 X : C O 2 ; Y : C H 2  CH  C OOH ; Z : CH 2  CH C H 2 OH ; C H O
2

H
|
Ph H (  ) CH 3CH 2 COH
|
| | CH3
Q.10 CH 3  C  COOH + CH 3  C  COOH     
conc. H 2SO 4 , 
| |
H Ph
(recemic mixture)
Ph H H H
| | | |
CH 3  C  C  O  C  CH 2 CH 3  CH 3  C  C  O  C  CH 2CH 3
| || | | || |
H O CH 3 Ph O CH 3
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 whinc are diastereoisomers of each other.
CH 2
||
Q.11 P : CH 3  CH 2  O  C  CH 3
Q : CH3CH2OH
R : CH 3  C  CH 3
||
O
when ethylene reacts with dil. H2SO4CH3CH2 is produced during rate determining step, whereas P
gives resonance stabilized intermediate.
CH 3 CH 3
| |
CH 3  CH 2  O  C  CH 3 CH 3  CH 2  O  C  CH 3
 
due to extra stability of intermediate the rate of reaction is very fast
OH
|
Q.12 X: CCCC Y: CCCC
| | |
C NH 2 C
Y is optically inactive.

Alcohols & Ethers [24]