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For JEE- Main & Advanced
CHEMISTRY FOR JEE MAIN & ADVANCED

Hydroxy derivatives

Aliphatic hydroxy derivatives Aromatic hydroxy derivatives

Alcohols have sp3 hybridized oxygen atoms, but the C – O – H bond angle in methanol (108.9°) is considerably
larger than the H – O – H bond angle in water (104.5°) because the methyl group is much larger than a hydrogen
atom. The bulky methyl group counteracts the bond angle compression caused by oxygen’s nonbonding pairs of
electrons. The O – H bond lengths are about the same in water and methanol (0.96 Å), but the C – O bond is
considerably longer (1.4 Å), reflecting the larger covalent radius of carbon compared to hydrogen.

•• •• •• ••

O O
H
H 104.5° H C 108.9° H
H
water H
methyl alcohol

(I) ALIPHATIC HYDROXY DERIVATIVES :

Hydroxy derivatives in which —OH is directly attached to sp3 C (Alcoholic compounds).
(II) Aromatic hydroxy derivatives :
Hydroxy derivatives in which —OH is directly attached to sp2 C or benzene ring (Phenolic compounds).
ALIPHATIC HYDROXY DERIVATIVES
(a) Classification according to number of —OH groups :
(i) Monohydric [one –OH]  CH3CH2—OH

(ii) Dihydric [two –OH]  CH2 CH2

OH OH

(iii) Trihydric [three –OH]  CH2 CH CH 2

OH OH OH

(iv) Polyhydric [n –OH]  CH2 CH -------------CH 2

OH OH OH

80
 ALCOHOL, PHENOL & ETHER

(b) Classification according to nature of carbon :

(i) p or 1° – alcohol  CH3CH2 – OH
(ii) s or 2° – alcohol  (CH3)2CH – OH
(i) t or 3° – alcohol  (CH3)3C – OH

ALCOHOLS
Structure of alcohol 3 :O: sp 3
sp
Alcohols are bent molecules. The carbon atom (linked with 3
sp 108.5° 1s
'O' atom of –OH group) is sp3 hybridised. The central 'O'
atom is also in sp3 state of hybridisation. The bond angle is H3C 3 H
sp 1s
108.50 . In sp3 hybridisation of O - 2s2,2px2 2py1 2pz1 orbitals
Structure of CH3OH
hybridised to form sp3 orbitals

In these four orbitals two containing one electron

each and two containing two electrons each. Orbitals
containing two electrons do not take part in bonding. Other
two half filled orbitals form  bond with s-orbitals of H -atom
and hybridised orbital of C-atom (O—C).

Due to lone pair effect the bond angle of tetrahedral oxygen

atom is lesser than normal tetrahedral structure (109028').

MONOHYDRIC ALCOHOL
GENERALMETHODS OFPREPARATION
(a) From alkanes (By oxidation) :

H / KMnO4
(CH3)3 C—H (CH3)3 C — OH
Δ

(b) From alkenes :

(i) By hydration :

H
CH3 — CH = CH2 H2O

(ii) By hydroboration oxidation :

BH3
CH3— CH = CH2 H2O2/HO CH3 CH 2 CH2 (1° alcohol)

OH
(iii) By oxymercuration demercuration :
(i) Hg(OAc)2,H2O
CH3—CH CH2 CH3 CH CH 3
(ii) NaBH4,HO

OH

81
CHEMISTRY FOR JEE MAIN & ADVANCED

1. Preparation and reactions of glycol :

(ii) aq. NaHCO3

CH2OCOCH3

HIO4

–CH2–OH

2. General Reactions of Glycer ol :

114
 ALCOHOL PHENOL AND ETHER

SOLVED EXAMPLES
Ex. 1 Give the IUPAC names for the following compounds. Chiral descriptions are not required.
OH
OH
(a) (b)

OH
(c) (d) Br

Sol. (a) 2-Methyl-4-phenylbutan-2-ol ; (b) trans-4-phenylbut-3-en-2-ol ; (c) Cyclohex - 3-enol ;

(d) 1-(cis-3-Bromocyclohexyl)propan-2-ol
Ex. 2 How will you carry out the following conversions ? You may use other organic compounds if necessary.
(a) CH3OH to CH3CH2OH (b) CH3CH2OH to CH3OH
(c) CH3CH2OH to HOCH2CH2OH (d) CH3CH2CH2CH2OH to CH3CH2CHOHCH3
(e) CH3CH2OH to CH3CH2CHOHCH3 (f) C6H5COCH3 to C6H5CH2 CH2OH
OH
OH
(g) CH3CH2OH to (C2H5)2CHOHCH3 (h) to
OH
OH
OH
(i) to (j) CH2 = CHCH2OH to CH2OHCHOHCHO
OH
I2, red P Mg
Sol. (a) CH3OH heat Et2O CH3MgI
KCN 1. CO2
2. H3O
1. LiAlH4 H3O + 1. LiAlH 4
CH3CH2 OH 2. HNO2 CH3CN heat CH3COOH 2. H3O
+ CH3CH2 OH

PCC 1. CH MgI
Alternatively, CH3OH HCHO 2. H O3 + CH 3CH 2OH
3

2 K Cr O
2 7 AgOH Br2 AgOH
(b) CH3CH2 OH H SO CH3COOH CH3COOAg CH3Br CH3OH
2 4, heat CCl4, heat
H2SO4 1. O 3 1. LiAlH 4
Alternatively, CH3CH2 OH CH2 = CH2 HCHO 2. H3O
+ CH3OH
170°C 2. Zn/H2O

H2SO4 dil. KMnO 4

(c) CH3CH2OH 170°C
CH2 = CH2 cold

H3O+ O2, Ag 1. OsO4

HOCH2CH2OH CH2 CH2 CH2OHCH2OH
200°C 2. Na2SO3,H2O
O

PBr3 alc. KOH

(d) CH3CH2CH2CH2OH CH3CH2CH2CH2Br heat
CH3CH2CH=CH2

1. H2SO4 OH
2. H 2O, heat
CH3CH2CH=CH2 CH3CH2CHCH3
1. (CH3COO)2Hg, H 2O
2. NaBH4 ()-Butan-2-ol

115
 ALCOHOL PHENOL AND ETHER

Exercise # 1 [Single Correct Choice Type Questions]

1. In the following reaction sequence
aq.H 2 SO 4 1.CH 3 MgI
Ph – C  CH  2+
 A  B
Hg 2.H O 2

the product (B) is :

Ph CH3

(A) PhCOCH3 (B) PhCH2CHOHCH3 (C) C (D) PhCH2COCH3

CH3 OH
2. Consider the following reaction.
O16
16 +
CH3 – C – O18 –C 2H 5 + H 2O 
H

Heat
The products formed in the reaction are
O16 O16

(A) CH3 – C – O16 H and C2H5O18H (B) CH3 – C – O18 H and C2H5O16H

O16 O18
(C) CH3 – C – O16 H and C2H5O16H (D) CH3 – C – O18 H and C2H5O18H

3. Consider the following reaction sequence,

O
1.CH 3 MgI POCl 3
  A  B
2.H 2 O Pyridine,0°C

The product (B) is-

CH3 CH3 CH2 CH3
(A) Cl (B) OPOCl2 (C) (D)

4. Consider the following reaction sequence

dil.KMnO 4 PCl5
CH2 = CH2  A  B
cold excess

The products (A) and (B) are, respectively :

(A) CH3CH2OH and CH3CH2Cl (B) CH3CHO and CH3CHCl2
(C) CH2OH CH2OH and CH2ClCH2Cl (D) CH2OHCH2OH and CH2OHCH2Cl

5. Consider the following reaction sequence,

HCl aq.KOH
CH3C  CH 
2 mole
 A 
Heat
B

The products (A) and (B) are, respectively,

(A) CH3CH2CHCl2 and CH3CH2CHO (B) CH3CCl2CH3 and CH3COCH3
(C) CH3CCl2CH3 and CH3C  CH (D) CH3CHClCH2Cl and CH3CHOHCH2OH

121
CHEMISTRY FOR JEE MAIN & ADVANCED

Exercise # 2 Part # I [Multiple Correct Choice Type Questions]

1. Which of these statements are correct about nucleophiles :
(A) Nucleophiles have an unshared electron pair and can make use of this to react with an electron deficient
species.
(B) The nucleophilicity of an element (as electron donor) generally increases on going down a group in the periodic
table.
(C) A nucleophile is electron-deficient species
(D) All good nucleophiles are good bases when we deal across the period.

2. The correct nucleophilicity order is/are :

(A) (CH3)3 O  > CH3  (B) CH3S > CH3SH
(C) CH3CH2CH2O > (CH3)3CO (D) (CH3CH2)3N > (CH3CH2)3P
3. Which of the following are correct regarding the products of the given reaction

Me
Me
H CN aqueous acetone
H H
H
Cl

OCH3

Me Me Me

Me Me H Me
H H
CN OH CN HO CN
H H H H H H
H H

OH H H

OCH3 OCH3 OCH3

(X) (Y) (Z)

(A) only X and Z are formed (B) Y > Z (amount) (C) X > Y (amount) (D) Y > X (amount)

H H
TsCl NaBr
4.   X  Y.. X and Y are :
Pyridine
CH3 OH

H H H Br H
H H
(A) X = (B) Y = (C) X = (D) Y =
||

CH3 OTs CH3 H OTs

CH3 Br

134
CHEMISTRY FOR JEE MAIN & ADVANCED

Exercise # 3 Part # I [Matrix Match Type Questions]

1. Match the column I with column II.
Column-I Column-II
(substrate + RMgX) (Product)
(A) HCHO (p) Tertiary alcohol
O
(B) CH3—C—CH3 (q) First ketone then 3° alcohol
(C) CH 3—CH—CH—CH3 (r) Secondary alcohol
O
(D) Ester (s) Primary alcohol

2. Match the column I with column II.

Column-I (Reaction) Column-II (Possible products)

(i) Hg(OAc)2/H2O
(A) —CH 3 (p) —CH 2OH
(ii) NaBH4

OH
(i) B2H6/THF
(B) CH2 (q) —CH3
(ii)H2O2OH

OH

(C) (r) —CH3

OH
(i) Hg(OAc)2/H2O
(D) —CH 3 (s) —CH3
(ii) NaBH4

3. Match the characteristics mentioned in Column –II with the reactions given in Column –I
Column–I Column–II

C 2 H 5 OH
(A)    (p) SN2

Br

(B) NaBr (q) Rearrangement

 
OTs
O
NaI
(C) H3C–CH– –S–O–CH2–CN   (r) SN1
OH O

aqueous NaOH
(D) HO CH Cl     (s) Walden Inversion
CH CH3
CH3

142
 ALCOHOL PHENOL AND ETHER

Exercise # 4 [Subjective Type Questions]

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

2. Complete tthe following reactions :

CH3 O
H 3C CH 3 MgBr
(a) SOCl2
  (b)  
H2O
OH H3C

3. Complete tthe follofing reactions :

Ph
OsO 4
(a) O HI
 (b)  
NaHSO 3

PCl5 +
KCN H 3O NH3 heat
4. C2H5OH   (A)   (B)    (C)   (D)   (E)

PBr5 KOH(Alc.) HBr NH3

5. CH3CH2CH2OH   (A)   (B)   (C)   (D)

6. t-butyl alcohol reacts less rapidly with metallic sodium than the primary alcohol. Explain why

7. Provide products in the following reactions :

SOCl2 Hg(OAc) 2 NaBH 4

(a) OH   (b)   
Pyridine CH 3OH

(c) mCPBA
 

8. Identify the products A and B giving proper explanation :

CH3 CH3
H+ CH ONa
CH3C––CH 2 + H2O18   
 A, CH3C––CH 2 + CH3OH 
3
 B
O O
9. Indicate bonds which are cleaved
I : in basic conditions II : in acidic conditions

CH3
H3 C––C––CH2
O
a b

149
CHEMISTRY FOR JEE MAIN & ADVANCED

Exercise # 5 Part # I [Previous Year Questions] [AIEEE/JEE-MAIN]

1. During dehydration of alcohols to alkenes by heating with concentrated H2SO4 the initiation step is
(1) Protonation of alcohol molecule (2) Formation of carbocation [AIEEE-2003]
(3) Elimination of water (4) Formation of an ester
2. Among the following compound which can be dehydrated very easily is : [AIEEE-2004]
H3 C H3C

(1) (2)
OH H3C OH

CH3
OH

(3) (4)
H3C CH3 H3C CH3
OH

3. The decreasing order of nucleophilicity among the nucleophiles : [AIEEE-2005]

O
|| -
-
(A) CH3C – O (B) (C) (D) H3C S–O
|| ||
O O
(1) (C), (B), (A), (D) (2) (B), (C), (A), (D) (3) (D), (C), (B), (A) (4) (A), (B), (C), (D)
4. Reaction of trans 2–phenyl –1 – bromocyclopentane on reaction with alcoholic KOH produces: [AIEEE-2006]
(1) 2–phenylcyclopentene (2) 1–phenylcyclopentene
(3) 3-phenylcyclopentene (4) 4-phenylcyclopentene

5. The main product of the following reaction is : [AIEEE-2010]

conc. H 2SO 4
C6H5CH2CH(OH)CH(CH3)2   
H5 C6 H C6 H5CH2 CH3
(1) C C (2) C C
H CH(CH3)2 H CH3
C6 H5 CH(CH3)2 H5C 6CH2CH2
(3) C C (4) C CH2
H H H3C

6. From amongst the following alcohols the one that would react fastest with conc. HCl and anhydrous ZnCl2, is
[AIEEE-2010]
(1) 2-Butanol (2) 2-Methylpropan-2-ol (3) 2-Methylpropanol (4) 1-Butanol

7. Consider thiol anion (RSΘ) and alkoxy anion (ROΘ). Which of the following statement is correct ? [AIEEE-2011]
(1) RSΘ is less basic but more nucleophilic than ROΘ.
(2) RSΘ is more basic and more nucleophilic than ROΘ.
(3) RSΘ is more basic but less nucleophilic than ROΘ.
(4) RSΘ is less basic and less nucleophilic than ROΘ.
8. An unknown alcohol is treated with the “Lucas reagent” to determine whether the alcohol is primary, secondary or
tertiary. Which alcohol reacts fastest and by what mechanism : [JEE (Mains) 2013]
(1) secondary alcohol by SN1 (2) tertiary alcohol by SN1
(3) secondary alcohol by SN2 (4) tertiary alcohol by SN2

152
 ALCOHOL PHENOL AND ETHER

MOCK TEST

SECTION - I : STRAIGHT OBJECTIVE TYPE

1. Consider the following reaction sequence,
HCl aq.KOH
CH3C  CH 
2 mole
 A 
Heat
B

The products (A) and (B) are, respectively,

(A) CH3CH2CHCl2 and CH3CH2CHO (B) CH3CCl2CH3 and CH3COCH3
(C) CH3CCl2CH3 and CH3C  CH (D) CH3CHClCH2Cl and CH3CHOHCH2OH
2. The final product (IV) in the sequence of reactions is :

CH 2 CH2
CH 3 CHOH PBr2 Mg O H2O
| I II III IV
CH 3 Ether

(A) CH3 CHOCH2 CH2 OH (B) CH3 CHCH2CH2Br

CH3 CH3

(C) CH3 CH CH2 CH2OH (D) CH3 CHOCH2 CH3

CH3 CH3

OH
CHCl +KOH
3. 
3
Product :

about above reaction the incorrect statement is

(A) The name of reaction is Reimer tiemann's reaction
(B) The intermediate in the reaction is dichloro carbene
(C) The final product is o-hydroxy benzaldehyde
(D) the final product is benzyl chloride
4. The products formed in the reaction are :

O
18 H2SO4
C6H5 C OH + CH3OH
Heat

O O
18 18
(A) C 6H 5 C OCH 3 and H2O (B) C6H5 C OCH3 and H2O

O
18 18
(C) C6 H5 C CH2OH and H2O (D) C6H 5OCH 3 , CO and H2O

157
 11th Class Modules Chapter Details

Physics Chemistry Mathematics

5 5 5
Modules Modules Modules

PHYSICS CHEMISTRY MATHEMATICS

Module-1 Module-1(PC) Module-1

1. Physical World and Units 1. Mole Concept 1. Basic Maths and Logarithm
& Dimensions 2. Atomic Structure 2. Quadratic Equation
2. Basic Maths & Vector 3. Chemical Bonding 3. Sequence and Series
3. Kinematics 4. Gaseous State
Module-2
Module-2 Module-2(PC) 1. Trigonometric Ratio and
1. Thermodynamics Identities
1. Newton’s Law of Motion 2. Trigonometric Equation
& Friction 2. Thermochemistry
3. Chemical Equilibrium 3. Properties & Solution
2. Work, Energy & Power of Triangle
4. Ionic Equilibrium
Module-3 Module-3
Module-3(IC)
1. Centre of Mass & Collisions 1. Periodic Table & Its Properties 1. Permutation & Combination
2. Rotational Motion 2. Redox Reaction & Equivalent 2. Binomial Theorum
3. Gravitation Concepts 3. Complex Number
3. Hydrogen & Its Components
Module-4 4. S-Block Module-4
1. Straight Line
1. Mechanical Properties 2. Circle
of Matter Module-4(OC)
1. Nomenclature of 3. Conic Section
2. Thermal Properties of Matter (Parabola,Ellipse & Hyperbola)
Organic Compounds
Module-5 2. Isomerism
3. General Organic Chemistry Module-5
1. Simple Harmonic Motion 1. Mathematical Induction
2. Wave Motion Module-5(OC) 2. Mathematical Reasoning
3. Measurement Error 1. Reaction Mechanism 3. Statistics
& Experiment 2. Hydrocarbon
3. Aromatic Hydrocarbon
4. Environmental Chemistry

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 12th Class Modules Chapter Details

Physics Chemistry Mathematics

5 5 5
Modules Modules Modules

PHYSICS CHEMISTRY MATHEMATICS

Module-1 Module-1(PC) Module-1

1. Solid State 1. Sets & Relation
1. Electrostatics
2. Solutions and 2. Function
2. Capacitance
Colligative Properties 3. Inverse Trigonometric Function
3. Electro Chemistry 4. Probability
Module-2
1. Current Electricity Module-2(PC) Module-2
2. Magnetic Effect of Current 1. Chemical Kinetics and
and Magnetism Nuclear Chemistry 1. Limit
2. Surface Chemistry 2. Continuity
Module-3 3. Differentiability
Module-3(IC) 4. Method of Differentiation
1. Electromagnetic Induction
2. Alternating Current 1. Metallurgy
2. P- Block Module-3
Module-4 3. Transition Elements 1. Indefinite Integration
(d & f block) 2. Definite Integration
1. Geometrical Optics 4. Co-ordination Compound 3. Area Under the Curve
2. Wave Optics 5. Salt Analysis & Qualitative
Analysis Module-4
Module-5
Module-4(OC) 1. Application of Derivative
1. Modern Physics
1. Alkyl Halides & Aryl Halides 2. Matrix
2. Nuclear Physics
2. Alcohol, Phenol & Ether 3. Determinant
3. Solids & Semiconductor
Devices 3. Carbonyl Compound
Module-5
4. Electromagnetic Waves
5. Principle of Communication Module-5(OC) 1. Differential Equation
1. Carboxylic Acid & Their 2. Vector & 3-Dimensional
Derivatives
2. Biomolecules & Polymers
3. Chemistry in Everyday Life

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