ALCOHOLS

 Tertiary Alcohols (30): In these alcohols the –

SYNOPSIS
OH group is attached with tertiary carbon atom
 Alcohols are the hydroxyl derivatives of They posses a general formula R3C-OH
hydrocarbons i.e., obtained by the replacement CH 3
of one or more H atoms R-H  -H
+OH
 R-OH
C2 H5 - C - OH
 The compound in which a hydroxyl group is Eg: Tert. amyl alcohol
attached to a saturated carbon atom are called CH 3

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alcohols.
Allyl alcohols: In these alcohols the –OH group
Eg:- 1)CH 3OH 2)C2 H 5OH is attached a sp3 hybridized carbon atom next to
 The compounds in which hydroxyl group is the carbon – carbon double bond i.e. to an allylic
attached to an unsaturated carbon atom of a carbon.
double bond are called ‘enols’.Eg;- H 2C=CH-OH
Classification: Alcohols are classified
according to the number of hydroxyl groups Eg: H 2C = CH-CH 2 -OH
present in their molecules. Allyl alcohol But-3-en 2-ol
 Monohydric alcohols contain one –OH group, Benzyl Alcohols: In these alcohols, the –OH
dihydric two and trihydric three, respectively. group is attached to sp3 hybridised carbon next
 Monohydric alcohols are further classified to an aromatic ring.
H
according to the hybridization of carbon atom
CH2OH C – OH C – OH
to which the –OH group is attached.
Compounds containing Csp -OH bond:
3 Eg:- CH3 CH3

In these alcohols the –OH group is attached to a Primary Secondary Tertiary

sp3 hybridised carbon atom of an alkyl group.  Hence, allylic and benzylic alcohols may be
These are further subdivided as follows primary, secondary or tertiary.
 Primary Alcohols (10): In these alcohols the Compounds containing Csp2-OH bond:
–OH group is attached with primary carbon atom In these alcohols, the –OH group is attached to
They posses a general formula RCH2OH. R may a carbon atom of the double bond, i.e., vinylic
be H in the first member and alkyl group in the carbon or to an aryl carbon.
rest of the members. Eg: H2C=CH-OH – Vinyl alcohol
Eg: HCH2OH Methyl alcohol CH 3

OH
CH3CH2OH Ethyl alcohol OH

CH3CH2CH2OH n – propyl alcohol

 0
Secondary Alcohols (2 ):In these alcohols the Phenol
O-Cresol
–OH group is attached with secondary carbon
Note:
atom.They posses a general formula R2CHOH.  When two or more hydroxyl groups are attached
CH 3 - CH - CH 3 CH 3 - CH - CH 2 - CH 3 to the same carbon atom, the compound is
Eg: usually unstable. This unstable compound
OH OH looses a water molecule and gets converted to a
Isopropyl alcohol Secondary butyl alcohol stable compound.
 IUPAC system: According to this system
OH  H2O
C 
 C=O alcohols are called alkanols.
OH Eg:- CH3OH Methanol
CH3CH2OH Ethanol
Unstable
CH3 - CH 2 - CH 2 - CH 2 - OH Butan – 1 - ol
 But inspite of having two hydroxyl groups to the
same carbon atom, chloral hydrate CCl3CH(OH)2 Isomerism: Alcohols may exhibit chain,
is a stable compound. The unusual stability of chloral positional and functional isomerism.
hydrate has been attributed to the –I effect of  Functional isomers of alcohols are ethers.
chlorine and to the formation of intramolecular CH 3 –CH 2 –CH 2 –CH 2 CH 3 –CH–CH 2
Eg: and | |
hydrogen bonds. OH CH 3 OH

are chain isomers

CH 3 –CH 2 –CH 2 –CH 2 CH 3 –CH–CH 2 –CH 3

OH
and OH
are position isomers
 CH3–CH2–OH and CH3–O–CH3 are functional
Nomenclature: There are three systems of isomers.
naming the alcohols.  Unsaturated alcohols and carbonyl compounds
are tautomers.
Common system: In this system alcohols are
named as alkyl alcohols i.e., the word alcohol CH3 –C=CH 2 and CH3 –C–CH 3
OH O
are tautomers.
is added to the name of alkyl group.
 In higher members, it is always indicated  Alcohols containing chiral centres can exhibit
whether the –OH group is attached to primary, optical isomerism.
secondary or tertiary carbon atom by prefixing  The simplest monohydric alcohol that can
‘n’ for primary, sec for secondary and tert for exhibit enantiomerism is butan–2–ol.
tertiary.
H
Eg; CH3OH Methyl alcohol |
CH3CH2OH Ethyl alcohol CH 3  C  OH
CH3CH2CH2OH n-propyl alcohol |
OH C2 H 5

| W.E-1:Identify the most stable conformer of glycol.

Sec.butyl alochol
CH 3  CH 2  CH  CH 3 Sol. Gauche form of glycol is most stable. This is
Carbinol system: The simplest monohydric due to intramolecular hydrogen bonding.
alcohol CH3OH is called carbinol.
 All other members are considered its alkyl O H
derivatives. O–H
 The alkyl groups attached to the carbon atom H
carrying –OH group are named in alphabetical
order.
H H
Eg:- CH3OH CH3CH2OH
Carbinol Methyl carbinol
H

Dimethyl carbinol W.E-2:Glycerol does not contain ....alcoholic group

Sol. Tertiary
 Preparation methods of Alcohols: 
R  Mg  X  R1CHO 
H / H 2O
 R  CH  R1
1. From Alkenes: It is an electrophilic addition
|
reaction .
OH
H 2 C = CH 2 + H 2 O   CH 3 - CH 2 - OH
+
H
20 alcohol
 In this reaction there is a possibility of formation R
of carbocation . |

OH R  Mg  X  R1COR11 
H / H 2O
 R1  C  R11
CH 3 - CH - CH = CH 2 
HOH
H+
 CH3 - C - CH 2 - CH 3 |
OH
CH 3 CH 3 0
3 alcohol
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3 methyl prop 2 ene 2 methyl 2 butanol

Aqueous alkali hydrolysis of alkyl halide:
By hydroboration oxidation of alkenes:It This reaction is a nucleophilic substitution
is used to get primary alcohol from terminal reaction and in the reaction nucleophile HO- ion
alkene.
becomes hydrated to give the substituted
 Reagent used in this method is diborane
product. R - Br + KOH (aq)  R - OH + KBr
followed by alkaline H2O2.
 The product obtained in this reaction seems to Reduction of Aldehyde and Ketone:
follow anti markownikoff’s addition of water Aldehyde on reduction with LiAlH 4 gives
over alkene. primary alcohol, whereas ketones gives
 Hydroboration is regioselective. secondary alcohols.
 With unsymmetrical alkenes, the boron atom
bonds to the less substituted carbon atom. H H3O R – CH – OH
 R – CH – O 
R – C = O    2

BH
H 3C  CH  CH 2 
3
 CH 3  CH  CH 2
H H
| | Primary
Aldehyde alcohol
H BH 2
 In this reaction borane serves as electrophile.  H 3O 
H
R – C = O  R – CH – O   R2 – CH2 – OH
Oxymercuration demercuration of
Alkenes: The addition of H2O over alkene R R
Secondary
without rearrangement follows Ketone alcohol
markownikoff’s rule. In this reaction reducing agent may be
 Reagent used is mercuric acetate followed by 1) Zn/ HCl 2) Na/C2H5OH
reduction with NaBH4.
3) LiAlH4 4) NaBH4
R  CH  CH 2 
1) Hg ( OAc )2 , H 2O2 , THF
2) NaBH OH 
 R  CH  CH 3 Note:NaBH4 is a selective reducing agent. It
4,

| reduces only aldehydes, ketones, carboxylic

OH acids without affecting C = C, N = N, esters,
(  Ac   C  CH 3 )
||
O
nitriles and nitro group.
 LiAlH4 is used to reduce carbonyl compounds,
Note:No carbocation is formed in hydroboration acids, esters, acid chlorides and anhydrides to
oxidation reaction and oxymercuration and
alcohols without normally affecting the double
demercuration reaction.
bond. However, the double bond gets reduced
From Grignard’s reagent: Treatment of when a phenyl group is present at β position.
carbonyl compound with RMgX followed by  

aicidic hydrolysis forms an alcohol with new Eg: C6 H 5  C H  C H  COOH 

LiAlH 4

C6 H 5  CH 2  CH 2  CH 2  OH
carbon – carbon bond.
 Hydrolysis of Ester: Esters on hydrolysis Absolute alcohol is 99.6 to 100% pure ethyl
gives acid and alcohol. alcohol.
RCOOR1 + H 2 O H
 R-COOH + R1 - OH
+
From Starch: A suspension of starch is made
or HO-
by heating with water at 50°C.
 Alcohols being more volatile than acid an hence  Germinated barley called malt is added. Malt
it can easily be separated by distillation. contains diastase, which converts starch to
Ester hydrolysis involves the cleavage of C–O
maltose.
– C – OR
1 2(C6H10O5)n + nH2O  DIASTASE
 nC12H22O111
bond of  The mixture is cooled to 30°C and yeast is
O added. An enzyme, maltase produced by yeast
By Fermentation:Decomposition of large converts maltose into glucose.
compounds into simple compounds by enzymes C12H22O11 + H2O  MALTASE
 2C6H12O6
derived by mirco organisms like yeast is called
 Zymase converts glucose to ethyl alcohol.
fermentation.
 Enzymes are biocatalysts which are non living C6H12O6  ZYMASE
 2CH3CH2OH + 2CO2
nitrogenous compounds.  Methyl alcohol is prepared from water gas
 They catalyse reactions taking place in living enriched with H 2 in presence of oxides of
organism and act as specific catalysts. Yeast is chromium and zinc. It is also prepared by the
a single cell microorganism. partial oxidation of methane.
From Molasses: Molasses is the mother liquor CO + 2H2 
ZnO, Cr2 O3 , 200atm,600K
 CH3OH
left after seperation of sugar from sugar cane
  2CH3OH
0
2CH4 + O2 Cu, 250 C,100atm
juice.
 It is black and viscous and still contains 20-40%  Mineralised methylated spirit : 90%
sucrose. rectified spirit +9% methyl alcohol +1%
 It is diluted with water so that the percentage of petroleum oil and a purple dye.
sugar in it is 10%.  Industrial methylated spirit : 95% rectified
 Then H2SO4 is added to maintain the pH at 4. spirit +5% methanol.
 Ammonium sulphate or phosphate is added  Denatured alcohol is unfit to consume as it
which serves as food for yeast. Then yeast is contains CuSO4, pyidine or methanol. Industrial
added and the mixture is taken and retained in alcohol is also made unfit for drinking by adding
large wooden tank for 2–3 days at 30°C – 40°C. methyl alcohol.
 An enzyme, invertase produced by yeast
converts sucrose into glucose and fructose. W.E-3:How acetylene is converted to ethyl alcohol?
C12H22O11 + H2O  INVERTASE
 C6H12O6 + Sol. Acetylene on hydration gives acetaldehyde,
C6H12O6 which on reduction gives ethanol.
 Another enzyme, zymase converts glucose and HC  CH + H 2 O 
HgSO4
 CH3 - CHO 
LiAlH 4
 C2 H5OH
H 2SO4
fructose into ethyl alcohol.
C6H12O6  ZYMASE
 2CH3CH2OH + 2CO2 W.E-4:How benzyl alcohol is obtained from benzyl
 The fermented solution contains 6–10% ethyl chloride ?
alcohol and is called wash or wort. Sol. Benzyl chloride on base hydrolysis gives benzyl
 This dilute solution on fractional distillation alcohol.
gives rectified spirit containing 93-95% alcohol.
 Generally 95-96% alcohol is called as Rectified CH2Cl CH2OH
spirit (or) industrial alcohol. 
aq.NaOH

 It is converted to absolute alcohol by drying on
treating with quick lime and then over calcium.
 Physical properties of Alcohols: addition compound with CaCl2, it cannot be used
 Alcohols have higher boiling points than for drying ethyl alcohol.
hydrocarbons, ethers, aldehydes and ketones of  Ethyl alcohol is obtained from starchy grains and
comparable molecular masses. Alcohols have so is called as grain alcohol and as it is a constituent
greater intermolecular attractions arising due to of wines, it is called as spirit of wine
intermolecular hydrogen bonds. The tendency
of formation of hydroegn bonds is
Chemical properties: The hydroxyl group
10  20  30 alcohols
present in alcohols is a very reactive group and
the characteristic reactions of alcohols are the
 The boiling points of alcohols increase with an
increase in molecular mass arising due to vander reactions of –OH group
Waals forces.  The reactions of hydroxyl group consists of
 Alcohols and ethers are functional isomers but either cleavage of C – O bond of the cleavage
the boiling point of alcohol is greater than of O – H bond.
corresponding ether due to formation of  ‘C – O bond is weaker in the case of tertiary
intermolecular hydrogen bonds. alcohols due to +I effect of alkyl groups while
Eg. Order of boiling points : Methanol < Ethanol O – H bond is weaker in primary alcohols as
< Propanol < Butanol. electron density increases between O – H bond
 In case of alcohols with same alkyl group, and hydrogen tends to separate as a proton.
boiling point decreases with increasing  Hence in O – H cleavage, the order of
branching. reactivity is Primary > Secondary > Tertiary
Eg. n–Butyl alcohol > Iso butyl alcohol > tert. and in C – O cleavage the order of reactivity
Butyl alcohol. is Tertiary > Secondary > Primary.
 Alcohols are soluble in water due to hydrogen  During O – H cleavage proton is given out
bonding between molecules of alcohol and showing that alcohols are acidic in nature.
water.  However, alcohols are weaker acids than water.
 Solubility in water decreases with an increase This is because the alkyl groups in alcohols have
in the size of non polar hydrophobic alkyl group, +I effect.
which resists dissolution.  Hence the following order is followed in the
Eg. Order of solubility : CH3CH2OH > acidic nature of alcohols.
CH3CH2CH2CH2OH > CH3(CH2)4CH2OH
CH 3OH > Primary alcohol > Secondary
 Among isomeric alcohols, solubility decreases
alcohol > Tertiary alcohol
with increase in surface area.
 In general the reactions of alcohols may be
Eg. tert. Butyl alcohol > Isobutyl alcohol >
divided into following three categories.
n–Butyl alcohol.
(a) Reactions involving the cleavage of O – H
 The boiling point of methanol is 670C.
bond [C – O – H]with substitution or removal
Methanol is highly poisonous in nature.
of hydrogen as proton(i.e., alcohols act as
Ingestion of even small quantities can cause
blindness and large quantities causes even death. nucleophiles)
 Ethanol is a sweet smelling colourless liquid. It (b) Reactions involving the cleavage of carbon
is soluble in water as well as organic solvents. – oxygen bond [C – OH] with substituion or
Its boiling point is 78.1°C removal of –OH group (i.e., aclohols acts as
 Ethyl alcohol has burning taste and burns with electrophiles).
blue flame. A mixture of 95.6% ethyl alcohol (c) Reactions involving both the cleavage of
and 4.4% water forms constant boiling mixture alkyl and the hydroxyl groups of the alcohol
called as azeotropic mixture. Since it forms an molecules.
 Reaction with Metals: Alcohols react with W.E-6:Assertion (A): Dehydration of alcohols can be
metal to form metal alkoxide and evolve H2. carried out with Conc H 2SO4 but not with
This reaction is acid – base reaction. conc.HCl.
1 Reason (R) : H2SO4 is dibasic while HCl is
R - OH + M  R - OM + H 2 (M = Na, K etc)
2 monobasic.
1
1) Both A and R are true and R is the correct
Eg: C 2 H 5OH + K  C 2 H 5OK + H 2 explanation to A
2
2) Both A and R are true and R is not the correct
 Metal hydrides react with alcohol and evolve
explanation to A
H2 gas.
3) A is true but R is false
R-OH + MH  R - OM + H2 (M = Na, K etc) 4) A is false but R is true
Dehydration of Alcohols: Alcohols when Sol. ‘2’
heated in presence of conc. W.E-7:Hydroboration-Oxidation of CH 3CH  CH 2
0
H2SO4 (170 – 180 C) or H3PO4, Al2O3 or P2O5 produces.
undergoes dehydration to form alkene.
1. CH 3CH 2CH 2OH 2. CH 3CH  OH  CH 3
Eg: CH 3 - CH 2 - OH   H 2 C = CH 2 + H 2O
0
H SO ,160 C
2 4

 Order of ease of dehydration of alcohols: 3. CH 3CH  OH  CH 2OH 4. CH 3COCH 3

30 > 20 > 10 Sol. ‘1’
 Stability order of alkene: More substituted
W.E-8:The compound which gives the most stable
alkene is more stable (due to hyper conjugation)
carbonium ion on dehydration.
 Ease of dehydration:
CH 3
CH 3 CH CH 2OH CH 3 C OH
OH > OH> OH 1.
CH 3
2.
CH 3

 Alcohols when heated with conc. H2SO4 at 383 3. CH 3CH 2CH 2CH 2OH
0
K (110 C) give dialkyl sulphate and at 413 K
(1400C) give ether. At 443 – 453 K (170 – CH 3 CH CH 2CH 3
0
180 C) they give alkene. 4.
OH
 Alcohols when heated with alumina (Al2O3) at
Sol. ‘2’.
513 – 523 K (240 –2500C) give ether and at 633
K (3800C) give alkene. Note:Primary alcohols undergo dehydration by E2
 No rearrangement takes place in E2 mechanism. mechanism(tertiary or neo carbon is not present
at  poistion) while secondary and tertiary
W.E-5: Predict the major product of dehydration alcohol undergo dehydration by E1 mechanism.
of each of:  Regardless the type of alcohol, however, strong
(A) (CH3)2C(OH)CH2CH3 acid is always needed to protonate the O atom
(B) (CH3)2CHCH(OH)CH3 to form a good leaving group.
(C) (CH3)C(OH)CH(CH3)2  With 10 alcohols, however, loss of the leaving
group and removal of a proton occur at the same
CH3 H3C CH3 time, so that no highly unstable primary
(A) and (B) H3C C CHCH 3 (C) C C carbocation is generated.
Sol.
H3C CH3
 Rearrangement in the Alicyclic ring:  Primary alcohols are oxidized to either aldehyde or
In case of cyclic alcohols whenever a to carboxylic acids by replacing either one or two
carbocation is formed outside the next carbon C – H bonds by C – O bonds.
atom of a ring, ring expansion may takes place.
Examples of ring expansion: R - CH 2 -OH 
[O]
 R-CHO 
[O]
 R-COOH
 Secondary
2 alcohols
6
are oxidized to ketones by
2 + + + one C – H bond by a C – O bond.
replacing
3
H 3 1 1
OH   6
R 2 - CH 5- OH   R2- C = O
 H2O Bond breaks at C1 and C5 [O]
4 5 New bond forms at C5 and C6 4
–
1° Carbocation
 Tertiary alcohols have no H atom on the carbon
2° Carbocation

with OH group, so they are not oxidized.

–H+

2 6
2 + + 3
+

3 1 1
OH 
H
 6
Bond breaks at C1 and C5
R
 H2O
4 5 New bond forms at C5 and C6 4 5 Cyclo hexene
 O 
– 2° Carbocation
R – C – OH  No reaction
1° Carbocation
–H+
R

Carbon bearing –OH

Cyclo hexene group do not have
hydrogens
Reaction with HX: The reaction of alcohols
with HX (X = Cl, Br) is a general method to  Oxidation with Ceric ammonium nitrate (CAN)
prepare primary, secondary and tertiary alkyl is a very selective reagent for the mild oxidation
halide. of primary alcohol. The reagent also oxidise
aromatic methyl group into – CHO.
CH 3 - CH 2 - OH  
HBr
 CH 3CH 2 Br + H 2 O
CH 3 - CH 2 - OH 
CAN
 CH 3 - CHO
 More substituted alcohols usually react more
CH2 – OH  HCO
rapidly with HX. HCO
CAN
3 3 CHO
 Order of reactivity of alcohols with HX is
Tertiary > Secondary > Primary.  Manganese dioxide (MnO2) is selective and
 Primary alcohols form R – X by SN2 reaction mild oxidant. It is specific for allylic and
while secondary and tertiary alcohols form R–X benzylic alcohols.
by SN1 reaction.
Because carbocation is formed in SN1 reaction H 2 C = CH - CH 2 - OH   H 2 C= CH - CHO
MnO 2

of secondary and tertiary alcohols with H X , Oppenauer Oxidation: The reaction involves
carbocation rearrangement is also possible. the oxidation of secondary alcohols with a
ketone and a base to the corresponding ketone
Reaction with PX5: The treatment of PX5 with
of the alcohol.
primary and secondary alcohols forms an alkyl
halide. R 2 - CH - OH 
Al(OCMe)
CH -CO-CH
 3
3
3

R- OH + PCl3  R - Cl + H 3PO3 R - CO - R + CH 3 - CH(OH) - CH 3

R- OH + PCl5  R - Cl + POCl3 + HCl Haloform reaction: Compounds having methyl

keto group react rapidly with halogen in presence
Oxidation of Alcohols: Alcohols are of a base to form haloform.
oxidized to carbonyl compounds depending on R - CO - CH 3 + 3X 2 + 4NaOH  CHX 3 + RCOONa
the type of alcohol and reagent.
 Ethyl alcohol gives positive haloform test.
 Oxidation occur by replacing C – H bond on NaOH  Cl2
the carbon bearing OH group by C – O bond. C2 H 5OH  NaOCl   CHCl3  HCOONa
 Secondary alcohols having –CH(OH)-CH3 group CH3
also give haloform test. |
2,2-dimethylpropan-1-ol CH3  C  CH 2 OH Primary
|
Esterification reaction: Treatment of a CH3
carboxylic acids with an alcohol in presence of
an acid catalyst forms an ester. This reaction is CH3
|
called a Fischer esterification. 2-methylbutan-2-ol CH3CH 2  C  OH Tertiary
|

R- COOH+R1 - OH  RCOOR1 + H 2 O
H 2SO 4
CH3
 This reaction is an equilibrium. According to
W.E-10:How are the following conversions carried
Lechatilier’s principle, it is driven to the right
out ?
excess of alcohol or by removing the water is it
is formed. (i) Propane   propan-2-ol
Note:Esterification of a carboxylic acids occur in the (ii) Benzyl chloride  Benzyl alcohol
presence of acid but not in the presence of base.
(iii) Ethyl magnesium chloride 
 Propan-1-ol
Base removes a proton from the carboxylic acids
forming a carboxylate anion, which do not react (iv) Methyl magnesium bromide  
with an electron rich nucleophile. 2-Methylpropan-2-ol
Br2
Sol. (i) CH 3  CH 2  CH 3   CH – CH – CH Br
Uses of Ethanol: propane  HBr 3 2 2

1. Ethanol is used to prepare alcoholic beverages CH3  CH  CH3

2. Ethanol is used as solvent in perfumes, paints, KOH (alc.)

 CH 3  CH  CH 2 
2  H O |
OH
varnishes, dyes etc. propene
propan  2  ol

3. Ethanol is used as preservative for biological

CH2Cl CH2OH
specimens.
4. Ethanol is used to prepare acetaldehyde, acetic
acid, chloroform, iodoform, ethyl iodide etc. KOH(aq.)

(ii) + KCl (aq)
5. Ethanol is used as antifreeze in car radiators,
spirit lamps and as antiseptic. Benzyl chloride Benzyl alcohol

6. Ethanol is used to prepare power alcohol and

H
natalite, a substitute to petrol. |
(iii) C 2 H5 MgCl + H  C  O 

MISCLLANEOUS SOLVED EXAMPLES ethyl magnesium methanal
chloride
W.E-9:Draw the structures of all isomeric alcohols
H H
of molecular formula C5H12O and give their OH
H 2O
H – C – OMgCl  H – C – OH + Mg
IUPAC names. Classify them as primary,
secondary and tertiary alcohols. C2H5 C2H5
Cl
Sol. The structures, IUPAC names and the propan-l-ol
classification of all isomeric alcohols of
molecular formula C5H12O are : CH3
|
(iv) CH3  C  O + CH3 MgBr ether


Pentan-1-ol CH3 -CH 2 -CH 2 -CH 2 -CH 2OH Primary propanone methyl magnesium
(acetone) bromide

Pentan-2-ol CH3  CH 2  CH 2  CH  CH3 ; Secondary CH3 CH3

| | OH
OH |
H
CH3  C  OMgBr 2 O
 CH3  C  OH + Mg
| Br
|
Pentan-3-ol CH3  CH 2  CH  CH 2  CH3 Secondary CH3 CH3
| 2  methylpropan  2 ol
OH (tert  butyl alcohol)
 METHODS OF DISTINGUISHING BETWEEN PRIMARY, SECONDARY
AND TERTIARY ALCOHOLS:

Test Primary alcohol Secondary alcohol Tertiary alcohol

Lucas reagent Does not form turbidity Turbidity is formed in 5 Turbidity is formed
Testing with a mixture of at room temperature to 10 minutes immediately
conc. HCl and anhyd. (turbidity is obtained
ZnCl2 only upon heating)

Catalytic dehydro- RCH2OH  Cu R R

RCHO RCHOHR  Cu
RCOR
3000 C 3000 C
genation R–C–CH3 Cu
300C
 R–C=CH2
(vapours of alcohol are An aldehyde is obtained A ketone is obtained OH
passed over hot metal)
An alkene is obtained
Oxidation RCH2OH RCHOHR R3COH (with less
(with acidified    number
RCHO RCOR RCOR of
permanganate or carbon
dichromate solution)    atoms)
RCOOH Two acids Two acids
(same number of carbon (with less number of (with less number of
atoms in the three carbon atoms) carbon atoms under drastic
compounds) conditions)

Victor Meyer test Nitrolic acid gives red Pseudonitrol gives blue No colour is obained
colour colour
Alcohol
HI RCH2OH R2CHOH R3COH
HI HI HI
Alkyl iodide
AgNO2 RCH2I R2CHI R2CI
Nitro compounds AgNO2 AgNO2 AgNO2
(i) HNO2 RCH2NO2 R2CHNO2 R2CNO2
HNO2 HNO2 HNO2
(ii) NaOH
NaOH
R–CH–NO2 R2C–NO2 No reaction

NO NO
NaOH
R–C–NO2 Blue colour

NOH
NaOH
R–C–NO2
– +
NONa
Red colour
 13. Primary,secondary and tertiary alcohols are
LEVEL-I (C.W) distinguished by
1) oxidation method 2) Lucas test
NOMENCLATURE 3) Victor Meyer’s method 4)all the above
1. 2,4-dimethyl -3-pentanol is a 14. The reaction between an alcohol and
1) primary alcohol 2) secondary alcohol carboxylic acid leads to the formation of
3) tertiary alcohol 4) dihydric alcohol 1) Aldehyde 2) Ester 3) Ketone 4) Paraffins
2. Which of the following is a tertiary alcohol 15. Alcoholic is beverages contain
1)  CH 3 2 CHCH 2OH 2) CH 3CH 2CH 2CH 2OH 1) Glycerol 2) Ethyl alcohol
3) Methyl alcohol 4) Isopropyl alcohol
3) CH 3CH 2CH 2OH 4)  CH 3 3 COH
16. Ethyl alcohol on oxidation with acidified
PREPARATION K2Cr2O7 gives
3. The enzyme which converts glucose to 1) CH3COCH3 2) HCOOH
ethylalcohol is 3) CH3COOH 4) HCHO
1) zymase 2) invertase 3) maltase 4) diastase Pd  BaSO4 / Quinoline
17. H  C  CH  H 2  A
4. Whichof the following is Lucas reagent
1) ammonical silver nitrate 2) Br2 / CCl4 
HCl
B KOHaq
C
Here the ‘C’ is
3) dry ZnCl2 / con. HCl 4) alk.KMnO4 1) Propane 2) Ethanol 3) Ethyne 4) Ethylene
5. Ethyl alcohol is the hydrolysis product of 18. A compound (X) of molecular formula C3H8O
1) C2H5Cl 2) CH3CHO 3) C2H4 4) C2H5 MgI can be oxidized to a compound of molecular
PROPERTIES formula C3H6O2 (Y), (X) is most likely an
6. 95% ethyl alcohol can be converted to 1) Aldehyde 2) Alcohol
100% ethyl alcohol by the following 3) Ether 4) Both 2 and 3
1) Magnesium chloride 2) Calcium oxide 19. Which of the following gives Iodo form test
3) Magnesium phosphate 4) Magnesium sulphate 1) CH3—CH2—CH2—OH 2) CH3—CH2—OH
7. In wash or wort possess ---- percentage of 3) CH3—CH(OH)—CH3 4) Both 2 and 3
ethyl alcohol 20. There are three alcohols x,y,z which have 2,1
1) 95% 2) 100% 3) 66.9% 4) 6 - 10% and 0 alpha hydrogen atom(s) respectively.
8. CaCl2 + C2H5OH —> CaCl2. xC2H5OH. ‘x’ is Which does not give Lucas Test immediately
1) 3 2) 6 3) 2 4) 1 1) x 2) y 3) z 4) all the three do not give test
9. Ethanol and Methanol are miscible in water
due to LEVEL -I (C.W) - KEY
1) Dissociation of water 2) Their acidic character 1) 2 2) 4 3) 1 4) 2 5) 1 6) 2 7) 4
3) Allyl groups 4) Hydrogen bonding 8) 1 9) 4 10) 4 11) 4 12) 4 13) 4 14) 2
10. To bring about dehydration of alcohols we
can use 15) 2 16) 3 17) 2 18) 2 19) 4 20) 1
1) Conc. H 2 SO4 2) Al2O3 3) ZnO 4) both 1,2 LEVEL -I (C.W) - HINTS
11. The reaction 2 ROH  2 Na  2 RONa  H 2
suggests that alcohols are 1.
1) basic 2) amphoteric
3) neutral 4) acidic 2.  CH 3 3 C  OH
12. Which of the following reaction conditions
are used for the conversion of ethanol to 3. Glu cos e 
Zymase
 ethyl alcohol
ethylene. 4. Lucas reagent is a mixture of
1) conc. H 2 SO4 / 700 C 2) dil. H 2 SO4 /1400 C Conc.HCl  anh ZnCl2
5. Alkyl halides on hydrolysis gives alcohols
3) dil. H 2 SO4 /1000 C 4) conc. H 2 SO4 /1700 C
6. CaO
7. 6  10% C2 H 5OH 7. Absolute alcohol cannot be obtained by simple
fractional distillation because
8. X=3
9. Ethanol and methanol form hydrogen bond with 1) pure C2 H 5OH is unstable
water 2) C2 H 5OH forms chemical bonding with water
10. Conc.H 2 SO4 and Al2O3 are dehydrating agents 3) Oxidation
11. acidic 4) it forms azeotropic mixture with water.
12. 1700 C , con H 2 SO4 8. The number of 10 , 20 and 30 alcoholic groups
13. any one in Mannitoal or Sorbitol are respectively
14. ROH  RCOOH   1) 2, 4 and 0 2) 1, 4 and 0
H
 RCOOR  H 2O
3) 2, 2 and 0 4) 2, 1 and 1
15. C2 H 5OH 9. An isomer of ethanol is
16. C2 H 5OH is 10 - alcohol 1) Methanol 2) Dimethyl ether
3) Diethyl ether 4) Ethyl glycol
17. A  C2 H 4 B  C2 H 5Cl C = C2H5OH 10. Which one of the following is a secondary al-
18. X  CH 3  CH 2  CH 2  OH  C3 H 8O  cohol ?
1) 2 - Methyl - 1 - propanol
Y  CH 3  CH 2  COOH  C3 H 6O2  2) 2 - Methyl - 1 - propanol
19. CH 3CO group is present 3) 2 - Butanol 4) 1 - Butanol
11. If the boiling point of ethanol (molecular
20. X= RCH 2OH ; Y= R2CHOH
weitht = 46) is 780 C , the boiling point of di-
ethyl ether (molecular weight = 74) is
LEVEL-I (H.W)
1) 1000 C 2) 780 C 3) 86 0 C 4) 34 0 C
1. Which of the following is a tertiary alcohol 12. The percentage of C2 H 5OH in wash is
1) Ethyl alcohol 2) Isopropyl alcohol (approximatly)
3) Neopentyl alcohol 4) 2-methyl 2-propanol 1) 95% 2) 10% 3) 50% 4) 75%
2. Glycerol does not contain ........ alcoholic 13. Which of the following alkenes when passed
group
1) 10 2) 20 3) 30 4) 10 and 20 through conc. H 2 SO4 followed by hydrolysis
with boiling water would give tert - butyl
PREPARATION alcohol ?
3. Which of the following enzyme converts 1) Ethylene 2) Isobutylene
maltose to glucose 3) Propylene 4) 1 - Butene
1) Invertase 2) Zymase 3) Maltase 4) Diastase 14. Which one of the following gases is liberated
4. Absolute alcohol is prepared from rectified when ethyl alcohol is heated with methyl
spirit by magnesium iodide ?
1) Steam distillation 2) Fractional distillation 1) Methane 2) Ethane
3) distillation with CaO &Ca 3) Carbondioxide 4) Propane
4) Simple distillation 15. Identify A and B in the following reaction
5. Reaction, CO  2 H 673 k ,300 atm ,/ Cr2O3  zno
2 g   C2 H 5  Cl A
 C2 H 5OH  B
 C2 H 5Cl
may be used for manufacture of : 1) A = aqueous KOH; B = moist Ag2O
1) HCHO 2) CH3COOH 2) A = alcoholic KOH ; B = aqueous NaOH
3) HCOOH 4) CH3OH
3) A = aqueous NaOH ; B = AgNO2
PROPERTIES
6. When wine is exposed to air it become sour 4) A = AgNO2 ; B = KNO2
due to 16. 23g of sodium will react with methanol to give
1) Oxidation of C2H5OH into CH3COOH 1) One mole of oxygen 2) 1/2 Mole of hydrogen
2) Bacteria 3) Virus 4) Formic acid formation 3) One mole of hydrogen 4) 1/4 Mole of oxygen
17. The correct order of decreasing basicity of 14. Methane
the following species is : 15. aq. KOH and AgOH
H 2O, OH  , CH 3OH , CH 3O  16. As per stoichiometry
17. OH   CH 3O   CH 3OH  H 2O
1) CH 3OH  H 2O  OH   CH 3O 
18. More acidic
2) OH   CH 3O   CH 3OH  H 2O 19. Chloroform
3) H2O  CH3OH  CH3O  OH  20. CH 3COOC2 H 5
4) OH   CH 3O   CH 3OH  H 2O
18. Which of the following alcohols is expected to
have the lowest pK a value ?
1) Ethanol 2) 2-Fluoro ethanol
3) 2,2,2-Trifluoroethanol 4) 2-Chloroethanol
19. Action of bleaching powder on ethyl alcohol
gives
1) Chloroform 2) Dichloromethane
3) Trichloroethane 4) Ethylenechloride
20. Which is formed when ethanol reacts with ace-
tic acid
1) CH 3COOC2 H 5 2) C2 H 5OC2 H 5
3) CH 3OCH 3 4) CH 3CH 2CHO
LEVEL -I (H.W) - KEY
1) 4 2) 3 3) 3 4) 3 5) 4 6) 1 7) 4
8) 1 9) 2 10) 3 11) 4 12) 2 13) 2 14) 1
15) 1 16) 2 17) 2 18) 3 19) 1 20) 1

LEVEL -I (H.W) - HINTS

1.  CH 3 3 C  OH
CH 2 OH
|
H-C-OH
2. |
is glycerol
CH 2 OH

3. Maltose  Maltase

 glu cos e
Rectified spirit CaO  Ca
4.  absolute alcohol.
5. Industrial preparation
6. Oxidation
7. azeotropic mixture.
8. On the basis of structure
9. Alcohols and ethers containing the same number of
carbon atoms are functional isomers
10. -OH group is on the secondary carbon
11. b.p of alcohol is greaterthan ether
12. ‘Wash’ contains about 10% ethyl alcohol
13. Isobutylene
 2. ALCOHOLS, PHENOLS & ETHERS
10. Which of the following on oxidation gives
ALCOHOLS ketone
1) CH3—CH2—CH2—OH
LEVEL-II (C.W)
2) CH3—CH2—OH

NOMENCLATURE 3) CH3—CH2—CH2—CH2—OH
1. Which one of the following pairs of 4) CH 3  CH  CH 2  OH
compounds are functional isomers of each |
OH
other
1) CH 3CH 2CH 2OH , CH 3CHOHCH 3 11. Compound A reacts with Na metal to give B.
A also reacts with PCl5 to give C. B and C
2) CH 3CH 2CH 2OH ,  CH 3 2 CHCH 2OH reacts with each other to give dimethyl ether.
3) CH 3CH 2 CH 2 OH , CH 3CH 2 CH 2 Cl Then A, B and C respectively are
4) CH 3CH 2CH 2OH , CH 3OCH 2CH 3 1) CH3OH, CH3ONa, CH3COCl
2) CH3OH, CH4, CH3Cl
2. Primary alcoholic group is
3) CH3OH, CH3ONa, CH3Cl
4) CH3Cl, CH4, CH3OH
1) -CH2OH 2)  C  OH 3) >CHOH 4) >C=O 12. Two organic compounds A and B react with
sodium metal and release H2 gas. A and B
PREPARATION react with each other to give ethyl acetate.
3. Ethyl alcohol containing 9.5% methyl alcohol The A and B are
and 0.5% pyridine is called 1) CH3COOH and C2H5OH
1) Spirit 2) Denaturated spirit 2) HCOOH and C2H5OH
3) Rectified spirit 4) Absolute alcohol 2) CH3COOH and CH3OH
4. Breaking of big organic molecules in the 4) CH3COOH and HCOOH
presence of enzymes is called
13. Which one of the following reagents is useful
1) Cracking 2) Pyrolysis
in converting 1-butanol to 1-bromobutane?
3) Fermentation 4) Oxidation
1) CHBr3 2) Br2 3) CH3Br 4) PBr3
PROPERTIES 14. Which of the following are the starting
5. Which alcohol is most reactive towards materials for the Grignard’s synthesis of
HCl in the presence of anhydrous ZnCl2 ? t-butanol?
1) primary 2) secondary 3) tertiary 4) all of these 1) CH3MgBr + CH3COCH3
6. Isopropyl alcohol on oxidation forms 2) CH3CH2MgBr + CH3COCH3
1) Ethylene 2) Acetone 3) CH3MgBr + CH3CHOHCH3
3) Ether 4) Acetaldehyde 4) CH3MgBr + (CH3)3CH
7. When tertiary butyl alcohol is passed over 15. Ethanol when reacted with PCl5 gave A,
reduced copper, the reaction taking place is
POCl3 and HCl . A reacts with silver nitrate
1) oxidation 2) reduction
3) dehydration 4) substitution to form B (major product) and AgCl . A and
8. When ethylalcohol reacts with Br2 in presence B are respectively
of red phosphorus the compound formed is 1) C2 H 5Cl , C2 H 5OC2 H 5 2) C2 H 6 , C2 H 5OC2 H 5
1) C2H6 2) PBr3 3) CH3Br 4) C2H5Br 3) C2 H 5Cl , C2 H 5ONO 4) C2 H 6 , C2 H 5ONO
9. Ethyl alcohol forms X CaCl 2. C2H5OH; Y 16. The order of reactivity of alcohols towards Na
MgCl 2. C2H 5OH and Z CuSO 4. C2H 5OH or K metal is
when C 2 H 5 OH reacts with respective 1. Primary > Secondary > Tertiary
anhydrous salts. Then 2. Primary < Secondary < Tertiary
1) X =3, Y = 3, Z = 2 2) X =3, Y = 6, Z = 3 3. Primary < Secondary > Tertiary
3) X =3, Y = 7, Z = 4 4) X = 4, Y = 4, Z = 4 4. Primary > Secondary < Tertiary
17. The order of reactivity of dehydration of
alcohol is 7.
1. 10  20  30 2. 10  20  30
P 
3. 10  20  30 4. 10  20  30 8. C2 H 5OH  Br2 
4 n
 C2 H 5 Br  HBr
18. The dehydration of 1-butanol gives 9. Addition reactions of C2 H 5OH
1. 1-butene as the main product
2. 2-butene as the main product 10. 20  or  30 alcohols on oxidation give ketone
3. equal amounts of 1-butene and 2-butene
11. A  CH3OH, B  CH3ONa, C  CH3Cl
4. 2- methylpropene
19. In the esterification reaction, the correct 12. A  CH 3COOH , B  C2 H 5OH
order of reactivity of alcohols is 13. Alcohols are converted into haloalkanes with
1. CH 3OH  CH 3CH 2OH   CH 3 2 CHOH Phophorous trihalides
14. Methyl magnesim bromide and acetone
2. CH 3OH   CH 3 2 CHOH  CH 3CH 2OH 15. A  C2 H 5Cl , B  C2 H 5ONO
3. CH 3CH 2OH   CH 3 2 CHOH  CH 3OH 16. The reactivity of alcohols with active metals is
30  20  10
4.  CH 3 2 CHOH  CH 3OH 2OH  CH 3OH
17. The correct decreasing order of dehydration of
20. The alcohol which gives the most stable
the given alcohols with acids like conc. H 2 SO4
carbonium ion on dehydration is:
1) (CH3)2 CHCH2OH 2) (CH3)3 C - OH is 30  20  10
3) CH3 CH2CH2 CH2 OH 4) CH3-CH-CH2CH3 18. The reaction occur with rearrangement as
21. Which of the following reactions will yield 20 carbocation is more stable than 10 carbo
propan-2-ol? cation.

1) CH  CH  CH  HOH  H 19. Correct order or reactivity is
2 3

2) CH 3  CHO 
CH MgBr / HOH
3
CH 3OH  CH 3CH 2OH   CH 3 2 CHOH
20. 30 carbonium ion more stable
3) CH 2O 
C 2 H 5 MgI / HOH

21. Acetaldehyde on reaction with Grignard reagent

Neutral KMnO4
4) CH 2  CH  CH 3   to give a secondary alcohol

LEVEL -II (C.W) - KEY

1) 4 2) 1 3) 2 4) 3 5) 3 6) 2 7) 3
8) 4 9) 2 10) 4 11) 3 12) 1 13) 4 14) 1 1. 2-Methylpentanol-1 is a
15) 3 16) 1 17) 4 18) 2 19) 1 20) 2 21) 2 1) 10 alcohol 2) 20 alcohol
0
3) 3 alcohol 4) enol
LEVEL -II (C.W) - HINTS 2. Primary alcohol cannot be prepared by the
1. Alcohols and ethers are functional isomers reduction of
whose MF is same 1) aldehyde 2) acid 3) ketone 4) ester
3. The two enzymes present in yeast that are
2. CH 2OH responsible for the formation of ethylalcohol
3. Denaturated spirit from molasses in the fermentation process are
4. Fermentation 1) Invertase, zymase 2) Invertase, diastase
5. Order of reactivity of alcohols towards Lucas 3) Zymase, diastase 4) Invertase, maltase
reagent is 30  20  10 4. An organic compound ‘A’ containing C,H and
O has a pleasant odour with boiling point 780C.
6. On boiling ‘A’ with conc H2SO4,a colourless
gas is released. The organic liquid ‘A’ is:
 1) C2H5 Cl 2) C2H5 COOCH3 4) Secondary > Primary > Tertiary
3) C2H5OH 4) C2H6 14. Match the following lists
5. When equal weights of methyl alcohol and List - I List - II
ethyl alcohol react with excess of sodium A) Ethlene 1) Natalite
B) Acetylene 2) Preservative
metal, the volume of H 2 liberated is more in
C) Ethanol 3) Hawker’s lamp
the case of D) Diethyl ether 4) Drug
1) C2 H 5OH 2) CH 3OH 5) Polyethylene
Correct match is :
3) Equal in both 4) H 2 is not liberated
A B C D A B C D
6. Which one of the following gases is liberated 1) 3 2 1 5 2) 5 1 2 3
when ethyl alcohol is heated with methyl 3) 5 3 2 1 4) 5 1 4 2
magnesium iodide ? 15. 3 moles of ethanol react with one mole of
1) Methane 2) Ethane phosphorous tribromide to form 3 moles of
3) Carbondioxide 4) Propane bromo ethane and one mole of X. Which of
7. Which one of the following alcohols is the following is “X”
expected to have the lowest P Ka value ? 1) H 3 PO4 2) H 3 PO2 3) HPO3 4) H 3 PO3
1) Ethanol 2) 2-Fluoro ethanol
16. Which of the following is most suitable
3) 2,2,2-Trifluoroethanol 4) 2-Chloroethanol.
method for removing the traces of water from
8. R  OH  HX  R  X  H 2O . ethanol ?
In this reaction, the reactivity of alcohols is 1) Heating with Na metal
1) Tertiary > Secondary > Primary 2) Passing dry HCl through it
2) Tertiary < Secondary < Primary 3) Distilling it with CaO 4) Reacting with Mg
3) Tertiary > Primary > Secondary 17. Which of the following compound gives
4) Secondary > Primary > Tertiary ethylmethyl ketone on oxidation ?
9. (CH ) CHOH  1) Propan -2-ol 2) Butan -1-ol
3 2
mild oxidation
 X 
(i ) CH3MgBr
H2O
Y 3) Butan - 2-ol 4) 2-methylbutan-2-ol
Here ‘Y’ is
18. In CH 3CH 2OH , the bond that undergoes het-
1) Iso butyl alcohol 2) Iso butylene
3) sec.Butyl alcohol 4) tert.Butyl alcohol erolytic cleavage most readily in reaction with
10. Haloform reaction is not given by ‘Na’ is
1) C  C 2) O  H 3) C  H 4) C  O
1) CH 3COCH 3 2) CH 3COC2 H 5
19. What are X and Y in the reaction
3) C6 H 5COC2 H 5 4) CH 3CHOHCH 3 H 2O / 
C2 H 4  H 2 SO4 800 C
 X  Y
11. What is the final product obtained when chlo-
rine LEVEL-II
reacts with ethyl
(H.W) alcohol in KOH? 1) C2 H 6 , C2 H 5OH 2) C2 H 2 , C2 H 5 SH
1) CHCl3 2) CCl3CHO 3) CH 3Cl 4) none 3) C2 H 5OSO3 H , C2 H 5OH 4) C2 H2 , CH3CHO

12. C2 H 5OH 
KMnO4 / H
X  Y
 20. Which one of the following contains
H 2 SO4
CSP 2  OH bond ?
CH 3COOC2 H 5 , X and Y respectively aree
1) vinyl alcohol 2) allyl alcohol
1) CH 3OH ; C2 H 5OH 2) CH 3CHO; CH 3OH 3) benzyl alcohol 4) carbolic acid
3) CH 2  CH 2 ; CH 3COOH 4) CH 3COOH ; C2 H 5OH LEVEL -II (H.W) - KEY
13. R  OH  HX  R  X  H 2O . In this reac- 1) 1 2) 3 3) 1 4) 3 5) 2 6) 1 7) 3
tion, the reactivity of alcohols is 8) 1 9) 4 10) 3 11) 1 12) 4 13) 1 14) 3
1) Tertiary > Secondary > Primary
15) 4 16) 3 17) 3 18) 2 19) 3 20) 1
2) Tertiary < Secondary < Primary
3) Tertiary > Primary > Secondary
 LEVEL -II (H.W) - KEY OH OH
1. Primary alcohol
2. Ketone 1) Na2Cr2O7 / H 2 SO4 2) Zn
3. Invertase, Zymase
4. Primary alcohol does not give turbidity (X) (Y) (X) (Y)
immediately with Lucas reagent.
5. Methyl alcohol
OH OH
6. CH 4
7. More acidic 3. Zn 4) Na2Cr2O7 / H 2 SO4
8. 3  2 1
0 0 0

9. tert. butyl alcohol (X) (Y) (X) (Y)

O

10. does not contain || group PREVIOUS EAMCET - KEY : 1) 2 2) 4

C  CH 3
11. Chloroform
12. CH 3COOH ; C2 H 5OH
NOMENCLATURE
13. Tertiary > Secondary > Primary
1. C

2
OH—CHOH—CH2OH is glycerol.
H

15. H 3 PO3 It doesn't contain ------------ alcoholic group

16. Distillation 1) 10 2) 20 3) 30 4) both 10 & 20
17. 2-Butanol 2. An example for a polyhydric alcohol is
18. O-H 1) Methyl alcohol 2) Neopentyl alcohol
19. C2 H 5OSO3 H , C2 H 5OH 3) Sec butyl alcohol 4) Mannitol
20. tert-butyl alcohol 3. Which one of the following is a secondary
alcohol
PREVIOUS EAMCET QUESTIONS 1) 2-methyl-2-propanol 2) 1-propanol
1. Identify the product in the following reaction 3) 1-butanol 4) 2-pentanol
OH PREPARATION
4. Ethyl alcohol is manufactured from ethylene
CHCl3 by
  Product 1) Permanganate 2) Catalytic oxidation
NaOH
3) Absorption into Conc. H2SO4 followed by
CHO OH hydrolysis 4) Reduction
CHO 5. Which of the following pairs of the compounds
can be used as starting materials in the synthesis
1) 2) of 2-phenyl-2-pentanol?
1) CH 3  CH 2 3 Br and PhCOOH
OH CO2H 2)  CH 3 2 CHCH 2 Br and PhCOCH 3
CO2H
3) PhBr and CH 3CH 2CH 2COCH 3
3) 4) 4) PhBr and  CH 3 2 CHCH 2COCH 3
6. An enzyme which brings about the
2. X Y
 Benzoquinone . Identify X and Y in conversion of starch into maltose is known
as
this reaction
1) Diastase 2) Zymase 3) Maltase 4) Invertase
7. Which is the catalyst in the conversion of water
gas and hydrogen into methyl alcohol?
1) MnO 2) raney Ni 3) Fe 4) ZnO-Cr2O3
 PROPERTIES ethyl chloride is formed. Mole ratio of PCl3
8. When ethyl alcohol is distilled with bleaching and PCl5 in the mixture is
powder and water then chloroform is
1) 3 :1 2) 1:1 3) 1: 3 4) 2 :1
obtained. The no. of moles of bleaching
powder needed in the preparation of one mole 17. When vapours of an alcohol are passed over
hot reduced copper, it gives an alkene. The
of chloroform is
alcohol is
1) 10 2) 5 3) 4 4) 2
1) Primary 2) Secondary
9. CH3OH + PCl3  A
3) Tertiary 4) None of these
A 
KCN
 B  
hydrolysis
 C .Then "C" is 18. When ethylhydrogen sulphate is heated with
1) CH3CH2OH 2) CH3CHO excess of alcohol at 410K, the product obtained
3) CH3COOH 4) CH2OH-CH2OH is
10. An organic liquid A containing H and O has 1) Ethane 2) Ethylene
a pleasant odour with a boling point of 780C. 3) Diethyl ether 4) Diethyl sulphate
On boiling A with conc. H2SO4 a colourless 19. How many primary alcoholic isomers are
gas is produced which decolourises bromine possibe for C5 H11OH ?
water and alkaline KMnO4. One mole of this
1) 5 2) 4 3) 2 4) 3
gas also takes one mole of H2. The organic 20. Methanol is industrially prepared by
LEVEL-III
liquid A is
1) C2H5Cl 2) C2H5CHO 3) C2H6 4) C2H5OH 1) Oxidation of CH 4 by steam at 900 0 C
11. A compound reacts with sodium and liberates 2) Reduction of HCHO using LiAlH 4
hydrogen and on oxidation gives ketone. The 3) Reaction HCHO with a solution of NaOH
formula of the compound could be.
1) CH3CH2OH 2) CH3CHOHCH3 4) Reduction of CO using H 2 and ZnO  Cr2O3
3)CH3CH2CH2OH 4) CH3CH2 CH2CH2OH 21.  CH 3 3 C  OH 
H SO
2
  CH 3 2 C  CH 2 ;
4

12. Iodoform cannot be prepared from This reaction takes place through
1) CH 3OH 2) C2 H 5OH 1) S N 1 mechanism 2) S N 2 mechanism
3) CH 3CHO 4) CH 3COCH 3 3) E1 mechanism 4) E2 mechanism
13. I2 produced when ozone reacts with moist KI
is used to convert C 2H 5OH to CI 3CHO. LEVEL-III - KEY
Number of moles of ozone required to convert 1) 3 2) 4 3) 4 4) 3 5) 3 6) 1 7) 4
1 mole of C2H5OH into CI3CHO is 8) 3 9) 3 10) 4 11) 2 12) 1 13) 3 14) 2
1) 1 2) 2 3) 4 4) 3 15) 1 16) 2 17) 3 18) 3 19) 2 20) 4 21) 3
14. A compound "X" of the formula C3H8O gives
iodoform test. On oxidation with acidified LEVEL-III - HINTS
K2Cr2O7, X gave Y. Y also gives iodoform 1. HO  CH 2  CH  OH   CH 2  OH is glycerol.
test. Then X and Y are
2. Mannitol is hexahydric alcohol
1) CH3CH2CH2OH, CH3CH2CHO
3. 2-pentanol
2) CH3CHOHCH3 ,CH3COCH3
4. It is an industrial method of preparation of ethyl
3) CH3CH2CHO, CH3CH2CH2OH alcohol.
4) CH3COCH3, CH3CHOHCH3 5. Bromobenzene
15. In the Victor-Meyer’s test, red colouration is 6. Diastase
shown by ZnO Cr2O3
7. CO  H 2   CH 3OH
1) 10 Alcohol 2) 20 Alcohol
8. Four moles of bleaching power needed in the
3) 30 Alcohol 4) Phenol prepration of one mole of chloroform
16. When a mixture containing PCl3 and PCl5 is
heated with ethyl alcohol, a total of 4 moles of
 5. Assertion (A): Ethyl alcohol is soluble in
9. CH 3OH 
PCl3
 CH 3Cl organic solvents
 A
Reason (R) : Ethyl alcohol is having non polar

 CH 3CN 
KCN H 2O
 CH 3COOH
 B C  ethyl group.
6. Assertion (A): The boiling point of C2H5OH
10. C2 H 4 decolourises bromine water and alkaline is less than that of H2O though the molecular
KMnO4 weight of C2H5OH is more than that of water.
11. 20  or  30 alcohols on oxidation give ketone
Reason (R) : C 2H 5OH molecules are not
highly associated through hydrogen bonding
12. group gives iodoform test as water is
7. Assertion (A): Dehydration of alcohols can be
13. C2 H 5OH  4 I 2  CI 3CHO  5HI carried out with Conc H2SO4 but not with
4( O3  2 KI  H 2 O  2 KOH  I 2  O2 ) conc.HCl.
14. X= secondary alcohol ; Y= ketone Reason (R) : H2SO4 is dibasic while HCl is
15. Primary alcohol monobasic.
16. 1:1
8. Hydroboration-Oxidation of CH 3CH  CH 2
17. Tertiary alcohol undergoes dehydration
18. Diethyl ether produces.
19. based on the structure 1. CH 3CH 2CH 2OH 2. CH 3CH  OH  CH 3
20. from CO and H2
21. E1 mechanism 3. CH 3CH  OH  CH 2OH 4. CH 3COCH 3
9. The compound which gives the most stable
LEVEL-IV
carbonium ion on dehydration.
1) Both A and R are true and R is the correct CH3
explanation to A CH 3 CH CH2OH CH
2) Both A and R are true and R is not the correct 1) 2) 3 C OH
explanation to A CH 3 CH3
3) A is true but R is false CH3 CH CH2CH3
4) A is false but R is true 3) CH 3CH 2CH 2CH 2OH 4)
1. Assertion (A): In the fermentation process of OH
molasses, along with yeast (NH 4 ) 2SO 4 , 10. An alcohol on oxidation gives CH 3COOH and
(NH4)3PO4 is added.
CH 3CH 2COOH . The alcohol is
Reason(R): (NH4)3PO4 and (NH4)2SO4, act as
food and helps the growth of yeast. 1. CH 3CH 2OH
2. Assertion (A): Alcoholic fermentation
involves conversion of sugar into ethanol by 2. CH 3CH  OH  CH 2CH 3
the action of yeast.
3.  CH 3 2 C  OH  CH 2CH 3
Reason(R): Fermentation involves the
liberation of CO2 gas. 4. CH 3CH  OH  CH 2CH 2CH 3
3. Assertion (A): Ethanol is miscible in all
11. An alcohol (A) on heating with concentarated
proportions with water
Reason (R) : Hydrogen bond is formed H 2 SO4 gives alkene (B) which can show the
between water and alcohol molecules. geometrical isomerism. The compound(A) is:
4. Assertion (A): CaCl2 can’t be used for drying 1) (CH3)2 C (OH) CH (CH3)2
ethyl alcohol 2) (CH3)2 C (OH) CH2 Me
Reason (R) : Calcium chloride can form an 3) CH3 CH2 CH (OH) CH3
addition compound with ethyl alcohol 4) All of the above
12. Which of the following compounds on reaction PREVIOUS MAINS QUESTIONS
with CH3 Mg Br Will give a teritiary alcohol? 1. Arrange the following compounds in order of
1) C2H5 CHO 2) HCHO decreasing acidity
3) C2H5 COOH 4) C2H5 COOCH3
13. 0.037g of an alcohol R-OH was added to OH OH OH OH
CH3MgBr and the gas evolved measured
11.2ml at STP.The molecular mass of
R--OH will be
1) 47 2) 79 3) 74 4) 77
Cl CH3 OCH3
LEVEL-IV - KEY
1) 1 2) 2 3) 1 4) 1 5) 1 6) 1 7) 2 (1) (2) (3) (4)

8) 1 9) 2 10) 4 11) 3 12) 4 13) 3 1) II > IV > I > III 2) I > II > III > IV
3) III > I > II > IV 4) IV > III > I > II
LEVEL-IV - HINTS
1. Ammonium phosphate and ammonium sulphate PREVIOUS MAINS KEY : 1) 3
act as food for yeast
2. Both are correct ADDITIONAL QUESTIONS
3. Ethanol is a associated with water through 1. What is the structure of  C4 H10O  which can
hydrogen bond. give positive haloform test and evolves
4. CaCl2 3C2 H 5OH hydrogen gas with LiAlH 4 .
5. Ethyl alcohol is soluble in polar and non polar
1) CH 3  CH 2  O  CH 2  CH 3
solvents.
6. Both are correct CH 3
7. with HCl R-Cl will form
8. 3CH 3CH  CH 2 
BH inTHF3
  CH 3CH 2CH 2 3 B 2)
CH 3  CH  CH 2  OH
  CH 3CH 2 CH 2 OH  H 3 BO3
3 H 2 O2
OH 
CH 3
9. 3 carbanium ion is most stable.
0

CH 3  CH  CH 2  CH 3
CH 3CH  OH  CH 2CH 2CH 3 
  CH 3  C  OH
O

10. 3) 4)
CH 3COOH  CH 3CH 2COOH OH
CH 3
11. A  CH 3CH 2CH  OH  CH 3 2. The relative rates of reaction with
B  CH 3CH  CHCH 3 concentrated H 2 SO4 of the following is
O I)
OH
|| OH OH
12.
CH 3  CH 2  C  OCH 3 
CH 3 MgBr
excess
?
II) III)
13. 11.2 ml of CH 4 at STP is formed by 0.037 g of
R-OH
1) I > II > III 2) II > I > III
22.400 ml CH 4 at STP .......? 3) I > III > II 4) II > III > I
0.037  22, 400 3. Which of the following is the best dehydrating
= = 74g of alcohol agent for 10 alcohols
11.2
1) Con H 2 SO4 2) CaO 3) Al2O3 4) POCl3
 CH3 CH3
OH
Con
NBS Ph C C Ph Product is

 8. H2SO4
4.
OH OH
Ph
Product (A) is Ph C C Ph
Ph C C CH3
OH O  Br 1) 2)
O O
O CH3
1) 2)
CH 3  CH  CH 2  Br CH 3  CH  CH 3 Ph
Ph C C CH3
O CH3 C C CH3
3) 4)
3) 4) CH 3  CH 2  CH 3 O Ph
O O
CH 3  C  CH 3
9. Which of the following alcohols is the least
5. What is the major of the following reaction? soluble in water?
O 1) Ethanol 2) 1-Propanol 3) 1-Butanol 4) 1-Pentanol
10. 3, 3-Dimethyl-2-butanol on reaction with
NaBH
HCl yields mainly

4  Products is
1) 2-Chloro-2, 3-dimethylbutane
2) 1-Chloro-2, 3-dimethylbutane
3) 2-Chloro-3, 3-dimethylbutane
OH OH 4) 1-Chloro-3, 3-dimethylbutane
11. Propylene is subjected to hydroboration
oxidation reaction. The product formed
would be
1) 2) 1)Propanal 2)1-Propanol 3)2-Propanol 4)Propanone
12. Ethylene glycol when heated in the presence
CO2H CO2H
of an hydrous ZnCl2 yields.
O O
1) Ethanal 2) Ethylene oxide
3) Dioxane 4) Diethylene glycol
13. Clear orange solution of chromic anhydride
3) 4) in aqueous sulphuric acid turn blue-green on
reaction with
1) 3-Methyl-3-pentanol 2) 2-Butanol
6. Which are not cleaved by HIO4 ? 3) 2-Methyl-2-propanol 4) 2-Methyl-2-butanol
I) glycerol II) glycol 14. An organic compound ‘X; on treatment with
III)1, 3-propenediol acidified K 2Cr2O7 gives a compound ‘Y’ which
IV)methoxy-2-propanol reacts with I 2 and sodium carbonate to form
1) I, II, III, IV 2) I, II
3) II, III 4) III, IV triodomethane. The compound ‘X’ could be
CH3 1) CH 3OH 2) CH 3CHO
NA2Cr2O7 3) CH 3CH  OH  CH 3 4) CH 3COCH 3
7. CH3 C CH3 ? 15. Fusel oil is a mixture of
Cool
OH
1) Ethers 2) alcohols
3) Alcohols and ethers 4) Alcohols and ketones
CH3 CH3 16. How many structuaral isomeric compounds
1) 2) are possible for C4 H10O ?
CH3 C CH2 CH3 CH CH3 1) 4 2) 5 3) 6 4) 7
CH3 CH3 i CH3Mgl
17.   X 
Cu /575 K
Y
ii H2O

3) CH 2 C O C CH3
4) No reaction The compound Y in the above sequence is
CH3 CH3 1) 2-Methyl-2-phenyl-1-propanol
 2) 2-Phenyl-2-propanol 3) Acetophenone 25. Rate of hydration of
4) 2-Methyl-1-phenyl-2-propanol
18. Which is the best reagent to convert isopropyl I) CH = CH2 II) CH = CHCH3
alcohol to isopropyl bromide?
CH 3 CH 3
III) CH = CH2
CH 3  CH  OH 
?
 CH 3  CH  Br
will be in order;
1) HBr 2) SOBr2 3) Br2 4) CH 3 MgBr 1) I<II<III 2) I<III<II 3) II<I<III 4) III<II<I
19. Choose the alcohol that is most reactive with 26. Glycerol

KHSO4
 A LiAlH 4
 B , A and B
conc. HCl / ZnCl2 ? are;
1) Methanol 2) Ethanol 1) Acrolein, allyl alcohol
3) 2-propanol 4) 2-methyl-2-propanol 2) Glyceryl sulphate, acrylic acid
20. Treatment of 3-methyl-2-butanol with 3) Allyl alcohol, acrolein
dry HCl gives 4) Only acrolein (B is not formed)
OH OH
27. 2 5 . In this dioal
Cl
1) 2)
Cl
1) OH at C2 is more basic than that of at C5
2) OH at C2 is more acidic than at C5 .
3) 4)
Cl 3) both have same basic strength
21. Glycol on treatment with PI 3 mainly gives 4) both have same acidic strength
28. Lucas test is used to make distinction between
1) Ethylene 2) Ethylene iodide
3) Ethyl iodide 4) Ethane 10 , 20 and 30 alcohols. This do not show that
22. Acrolein is formed when glycerol is heated 1) ROH behaves as a base
with 2) greater the value of pK a (alcohol), greater
1) Acidified KMnO4 2) Br2 water the reactivity with conce. HCl and thus sooner
3) KHSO4 4) HNO3 the formation of white turbidity.
3) alcohol which reacts fastest with Na metal,
23. Glycerol on treatment with oxalic acid at will give turbidity at fastest rate
1100 C forms 4) alcohol which gives red colour during Victor
1) Allyl alcohol 2) Formic acid Mayor test, will give turbidity ast slower rate
3) CO2 and CO 4) Glyceric acid then those giving blue or white colour during
24. If the starting material is 1-methyl-1, Victor Mayor test.
2-epoxy cyclopentane, of absolute 29. Match the column:
configuration, decide which one compound Column -I Column - II
correctly represent the product of its reaction A) Oxidation of 10
with sodium methoxide in methanol. alcohols in aldehyde P) KMnO4 / 

CrO3. .HCl
1) 2) B) Q) Collin’s reagent
OCH3 CH3O CH3
HO CH3 OH N

CrO3.2
3) CH3 4) C) R) Jone’s reagent
OH
CH3O CH3O CH3
N
 D) Oxidation of alkene into acid
S) P.C.C
CH 3  CH  CH  CH 2 
Reagent R
 Alcohol
30.
CH 3
Which is true about alcohol and R?
Alcohol Reagent
C H 3  C H  C H 2  C H 2O H

A) B2 H 6 , H 2O2 / NaOH
CH 3
CH 3  CH  CH  CH 3

B) PdCl2 , H 2O, O2 / LAH

CH 3 OH

OH

C H 3  C  C H 2C H 3
C) Hg  OAc 2 , H 2O / NaBH 4
CH 3
OH

C H 3  C  C H 2C H 3
D) dil. H 2 SO4
CH 3

ADDITIONAL QUESTIONS - KEY

1) 3 2) 4 3) 4 4) 3 5) 1 6) 4 7) 4
8) 3 9) 4 10) 1 11) 1 12) 4 13) 2 14) 3
15) 2 16) 4 17) 3 18) 2 19) 4 20) 2 21) 1
22) 3 23) 2 24) 2 25) 1 26) 1 27) 1
28) 1, 2, 4
29) (A) Q, R, S (B) S (C) Q (D) P 30) A, B, D
ADDITIONAL QUESTIONS - HINTS
1. 2-hydroxy-2-alcohols responds to haloform
reaction
2. Stability of alkene in driving force
3. POCl2 is better leaving group
4. NBS is oxidising agent
5. H  attack on can less hindered side
6. 1,2 diols oxidised by HIO4
7. 30 alcohols do not undergoes oxidation
9. as the Bulkyness increases solubility decreases
10. 1, 2 alkyl shift
11. anti markoniv’s addition of H 2O
13. 10 and 20 alcohols oxidised by K 2Cr2O7 / H 
 ETHERS
Formula name Common name IUPAC
SYNOPSIS
CH 3OCH 3 dimethyl ether methoxy methane
 The substitution of a hydrogen in a hydrocarbon
by an alkoxy or aryloxy group produces ethers. CH 3OC2 H 5 ethylmethylether methoxy ethane
 General formula of ethers Cn H 2n  2O which is C2 H 5OC2 H 5 diethyl ether ethoxy ethane
similar to that of monohydric alcohols.
CH 3OC3 H 7 methylpropylether methoxy propane
 Ethers are alkyl (or) Aryl derivatives of alcohol
(or) phenols, also treated as di alkyl derivatives C2 H5OCH CH3 2 ethyl isopropylether 2-ethoxy propane
of water.
C6 H 5OCH 3 Anisole Anisole
 The general formula of ethers : R  O  R ' .
' Few more examples
 R and R are alkyl, alkenyl or aryl groups. If
Compound IUPAC name
the R and R ' are same it is called simple or
CH3 CH3
symmetrical ether.
Ex:- CH 3OCH 3 , C2 H 5OC2 H 5 OC2H5 2-Ethoxy-1,
' 1-dimethylcyclohexane
 If R and R are different it is called mixed or
unsymmetrical ether.
C6 H 5OC6 H 5 Phenoxy Benzene
Ex:- CH 3OC2 H 5 , CH 3OC3 H 7
' OCH3
 If R and R are alkyl groups those are known as
|
aliphatic ethers. 1, 1 - Dimethoxy ethane
CH3  CH  OCH3
Ex:- CH 3OCH 3 , CH 3OC2 H 5
' CH3O  CH 2 3 OC2 H5 1-Ethoxy-3-methoxy propane
 If both R and R are aryl groups those are known
as di aryl ethers.  Cyclic ethers are known as oxiranes, these are
Ex:- C6 H 5OC6 H 5 named as alkyl oxirane (or) epoxy alkane
 If one is alkyl other one is aryl those are known
as phenolic ethers. Ex: Oxirane (or) Epoxy ethane
Ex:- C6 H 5OCH 3
 Ethers are considered to be dialkyl derivatives
of water. 2-methyl oxirane (or)
Nomenclature
 Ethers are named in two ways 1,2-epoxy propane
a) common system and b) IUPAC system
 In common system, ethers are named after alkyl 2,3-dimethyl oxirane (or)
groups attached to oxygen atom.
 For simple ethers , the common name is di alkyl 2,3-epoxy butane
ether.For mixed ethers, the common name is
alkyl, alkyl ether.Ethers are named first in the Structure of Functional Group: In
alphabetical order followed by the word ether ethers, the four electron pairs, i.e, the two bond
in common system. pairs and two lone pairs of electrons on oxygen
 In IUPAC system, ethers are named as alkoxy are arranged approximately in a tetrahedral
alkanes. The smaller alkyl group along with arrangment. The bond angle is slightly greater
oxygen atom is taken as alkoxy part while the than the tetrahedral angle due to the repulsive
larger alkyl group as alkane part. interaction between the two bulky alkyl groups.
 The C-O bond length (141 pm) is almost the 
iii) CH3 CH2 O CH2CH3  CH3 CH2 -O-CH2CH3+H+
same as in alcohols. 
H
 Above method is suitable for the preparation of
ethers having primary alkyl groups only and
110° alkyl group should be un hindered, temperature
CH3 CH3
be kept low.
Isomerism in Ethers  If alcohol is secondary or tertiary,elimination
 Functional Isomerism : Ethers are functional competes over substitution, which forms alkene
isomeric with monohydric alcohol (ii) Williamson’s Synthesis: By this method
Ex: 1) C2 H5OH and CH 3OCH 3 symmetrical and un symmetrical ethers can be
prepared.
2) C3H 7 OH and C H 3 O C 2 H 5
 Alkyl halide reacts with sodium or potassium
3) C6 H 5CH 2 OH and C6 H5OCH3 alkoxide to form ether. The reaction involves
 Metamerism: Ethers with minimum four SN2 attack of an alkoxide ion on primary alkyl
carbons can exhibit metamerism halide.
' '
Ex: Compound with molecular formula C 4 H10 O RX  R ONa  RO R  NaX
has three isomers C2H5ONa+IC2 H5  C2 H5OC2 H5  NaI
CH3OC3H 7 , C2 H5OC2 H5 , CH3OCH  CH3 2  For better yield of ethers alkyl halide preferred
is primary and alkoxide preferred is tertiary
Preparation methods of ethers  In case of secondary and tertiary alkyl halides
(i) By dehydration of alcohols: Alcohols elimination competes over substitution hence
undergo dehydration in the presence of protic product will be alkene
acids  H 2SO4 , H3PO4  . The formation of product  Order of reactivity of alkyl halides towards
alkene or ether depends on the reaction Williamson’s synthesis is 10  20  30
conditions.  Phenolic ethers can not be prepared from Aryl
 Ethanol is dehydrated to ethene in the presence halides due to their less reactivity towards
of sulphuric acid at 443K and at 413K nucleophilic substitution reaction.
ethoxyethane is the main product
WE-1: CH 3 Br  NaO  C  CH 3 3
 C2 H 5OH  HOC2 H 5 
conc. H 2 SO4
413 K
C2 H 5OC2 H 5  H 2O

C2 H 5OH 
H 2SO 4
443K
 CH 2  CH 2 CH 3
|
 The catalytic dehydration of ethanol with  CH 3  O  C  CH 3  NaBr
Al2O3 at 250  260 C also gives diethyl ether |
CH 3
2C2 H 5OH 
Al2O3
2600 C
 C2 H 5OC2 H 5  H 2O
 The formation of ether is a nucleophilic WE-2:  CH 3 3 C  Br  CH 3ONa 
bimolecular substituion reaction (SN2) involving
CH 3  C  CH 2  NaBr
the attack of alcohol molecule on a protonated |
alcohol, as indicated below: CH 3
i) CH3-CH2-O-H + H+  CH3-CH2-O+H2
 Alkoxides are not only nucleophiles but also
ii) CH3CH2-OH + CH3 - CH2 - O+H2 

acts as strong bases.
CH3 CH2 O CH2CH3
 
WE-3: CH C  ONa  C H Cl 
3 3 2 5

H  CH3 3 C  O  C2 H5
 Phenols are also converted to ethers by this Test for purity: Before using ether as
method.
anaesthetic, its purity is tested with FeSO4 and
OH KCNS, formation of blood red colour indicates
the presence of peroxide. That sample of ether
 R X
having peroxide can not be used as anaesthetic.
+ NaOH  
Chemical properties: Ethers are less reactive
 Williamson synthesis is not applicable if both than alcohols due to non-availablity of active
groups are phenyl or tertiary or vinyl groups. hydrogen.
 Ethers react with acids, phosporous halides,
WE-4:From chloroethane, 2-chloropropane and oxidising agents and reducing agents at high
chloro ethene, which is more reactive towards temperatures but cannot react with metals like
Williamson’s synthesis. sodium.
Sol. Chloroethane is more reactive, which is 10 R-  Reactions of ether are classified into three types
X. Where as 2-chloropropane is 20 R-X. In  Alkyl groups which undergo substitution
reactions
chloro ethene chlorine attached to high EN sp 2  Ethereal oxygen which co-ordinates with
carbon electron deficient molecules like Lewis acids.
(iii) From dry silver oxide  Carbon- oxygen bond which shows some
cleavage reaction.
2R  X  Ag 2O  R  O  R  2AgX
dry Reactions involving cleavage of C–O bond
Exclusive JEE-ADVANCE  Action of sulphuric acid
Ethers also can be prepared from alcohols and C2H5 – O – C2H5 + H2SO4(conc.)  

diazomethane C2H5OH + C2H5HSO4
  Action of HX
R  OH  CH 2 N 2   R  O  CH 3  N 2
BF3 (or)HBF4
R  O  R  HX  RX  ROH
Physical properties: Ethers are polar in ROH  HX  RX  H 2O
nature whose dipole moment(  ) is not equal  In the cold condition
to zero C2H5 – O – C2H5 + HI  C2H5I + C2H5OH
 Boiling point of ethers is less than their isomeric  In the hot condition with excess of HI
alcohols due to presence of hydrogen bond in
alcohols. C2H5 – O – C2H5 + 2HI    2C2H5I + H2O
 Smaller ethers miscible with water due to  Order of reactivity HI > HBr > HCl
hydrogen bond with water molecule Case-1: If both alkyl groups are different, nucleophile
 Dimethyl ether, ethylmethyl ether are gases attacks on smaller alkyl group
 Other ethers are colourless, highly volatile Ex: CH 3OC 2 H 5  HI  
S 2
N
 CH 3 I  C 2 H 5OH
liquids. Case-2: If one of the alkyl group is tertiary group
 Diethyl ether has characterstic pleasant odour major product is tertiary alkyl halide
and produce temporary unconsciousness when
Ex:  CH3 3 C  O  CH3  HI 
SN 1
vapour is inhaled.
 Ethers are slightly soluble in water and readily
CH 3OH  (CH 3 )3 CI
soluble in organic solvents due to lack of H-
bonding. Boiling point of Diethyl ether is less Case-3: Alkyl aryl ethers are cleaved at the alkyl-
than its functional isomer butyl alcohol oxygen bond due to the more stable aryl-oxygen
(C4H9OH) bond.
 Di ethyl ether and Butanol are alomost soluble OR
in water to same extent due to Hydrogen
Bonding.
Ex:
 Even both Alkyl groups are same in ether those + HX +R–X
are polar due to bent shape.
 Alkyl aryl ethers are cleaved at alkyl-oxygen  Friedel-Crafts reaction
bond due to the more stable aryl oxygen bond OCH3
and partial double bond character hence phenols
are formed. CH 3Cl 
Anhyd . AlCl3
 +
CS2

CH 3
|
WE-5: CH3  CH 2  CH  CH 2  O  CH 2  CH 3  HI 2-Methoxy- 4-Methoxy-
toluene toluene
 (Minor) (Major)

OCH3
CH3
|
CH3  CH2  CH  CH2  OH  CH3  CH2 I CH 3COl 
Anhyd . AlCl3
 +

WE-6: C6 H 5CH 2  O  C6 H 5  HI  2-Methoxy

COCH3
4-Methoxy
acetophenone
(Minor) acetophenone
C6 H 5CH 2 I  C6 H 5OH (Major)

Uses: Ether is used in /as

WE-7: Give an example of an ether which can not  a solvent for oils, fats, waxes, plastics etc.
 the extraction of organic compounds from
be decomposed by HI. Ex: Diphenyl Ether
aqueous solutions.
Electrophilic aromatic substitution on  an inert medium for various reactions (ex.Wurtz
anisole: In aromatic ethers alkoxy group is ring reaction) and preparation of RMgX
 an anaesthesia in surgery without causing any
activating group and increases electron density
damage to heart or lungs. (Recently,
of benzene ring at ortho and para positions
HALOTHANE is widely used for this purpose
 Hence electrophile attacks on ortho & para since it is harmless and quick in action. )
positions only.
Halothane CF3CHC Br (IUPAC name : 2-
 Halogenation: Phenylalkyl ethers undergo
Bromo-2- chloro-1,1,1-trifluroethane)
usual halogenation in the benzene ring. It is due
 NATALITE(mixture of alcohol and ether), a
to the activation of benzene ring by the methoxy
substitute for petrol
group. Para isomer obtained in 90% yield.
 Refrigerant along with dry ice (solid CO2 )
OCH3
which produces a temperature around 110 C
Br in Estimation of number of alkoxy groups by

ethanoic 
2
+ Zeisel method
acid
This method is used for the estimation of number
of alkoxy groups in ethers by reaction with HI
Anisole p-Bromoanisole O-Bromoanisole followed by AgNO3 solution. From this weight
(Major) (Minor) of AgI formed is calculated to determine the
 Nitration number of alkoxy groups.
OCH3 R  O  R  2HI  2R  I  H 2O
2RI  2AgNO3  2AgI  2RNO3
H 2 SO4

HNO3 
+
WE-8: From ether and alcohol which can be dried
over sodium metal.
Sol. Ether, it has no reaction with sodium metal
2-Nitroanisole 4-Nitroanisole where alcohol reacts with sodium metal and
(Minor (Major) liberates hydrogen gass
WE-9: How ethanol is distinguished from ether  Oxidation
Sol. By Iodoform test, sodium metal C2H5O C2H5 + (O) 
acid . K 2Cr2O7
 2CH3 CHO
Exclusive for JEE - ADVANCE 
acid . K 2Cr2O7
 2CH3COOH
 Reactions of alkyl group (Halogenation):  Dehydration
Diethyl ether reacts with chlorine or bromine to
C2H5O C2H5 
0
form halogen substituted ethers.Hydrogens at
Al2O3 / 360 C
 2CH2 = CH2 + H2O
 carbon atoms are easily substituted in the dark
condition. LEVEL-I (C.W)
Cl2
CH2OCH2CH3 
C H

3 Dark NOMENCLATURE
  1 1. The compound which is not isomeric with
CH 3 - C H (Cl) - O - C H(Cl) - CH 3 diethyl ether is
(  ,  ' dicholoro diethyl ether) 1) Butanone 2) Methyl propyl ether
3) 2-methyl propane-2-ol 4) Butanol-1
Cl
CH3CH2OCH2CH3 
Sunlight 
2
2. The number of metameric ethers possible
with the formula C4H10O are
C2Cl5 – O – C2Cl5
1) 4 2) 3 3) 2 4) 5
(perchloro diethyl ether)
3. The IUPAC name of C2H5 O C2H5
 Reactions of ethereal oxygen 1) Diethyl ether 2) Ethoxy ethane
C2 H5  O  C2 H5  (O)  C2H5 OC2H5 3) Ethoxy propane 4) Dimethyl ether

O PREPARATION METHODS
(Peroxide) 4. Phenol on heating with NaOH followed by
 Formation of oxonium Salts reaction with alkyl halide gives
  
1) Acetone 2) Ether 3) Ethanol 4) Acetic acid
C2H5–O– C2H5 + HBr  C2 H5  O  C2 H5  Br

5. Ethers are obtained by
 H 
1) Reaction of alkyl halide with dry ZnO
Diethyl oxonium bromide 2) Reaction of alkyl halide with moist ZnO
   3) Reaction of alkyl halide with dry Ag2O
C2H5  O C2H5  H2SO4 C2H5  O C2H5  HSO4 4) Reaction of alkyl halide with moist Ag2O

 H 
Diethyl oxonium hydrogen sulphate PROPERTIES AND USES OF ETHERS
 Hydrolysis 6. Following one is formed when a diethyl ether
is exposed to air for longer period
C2H5 – O – C2H5 + H2O  2C2H5OH
1) Ethyl alcohol 2) Acetaldehyde
(steam) 3) Ethylene 4) Peroxide of diethyl ether
 Action of PCl5 7. The compound which has the lowest boiling
C2H5 – O – C2H5 + PCl5  2C2H5Cl+POCl3 point is
CH 2  CH 2
 Action of acetyl chloride and acetic 1) H2O 2) C2H5OH 3) 4) CH3OCH3
anhydride OH OH
8. Total number of lone pair of electrons around
C2H5 – O – C2H5 + CH3COCl 
AlCl3
 oxygens in diethyl peroxide is / are
C2H5Cl + CH3COOC2H5 1) 2 2) 3 3) 4 4) 0
9. Ethyl chloride reacts with sodium ethoxide
C2H5 – O – C2H5 + (CH3CO)2O 
ZnCl2
 to form a compound (A). Which of the fol-
2CH3COOC2H5 lowing reactions also yields (A)?
 Action of carbon monoxide 1) C2 H 5Cl , KOH  alc  , 
C2H5–O–C2H5+ CO 
0
BF3 /150 C
500 atms
 C2H5COOC2H5 2) 2C2 H 5OH , conc.H 2 SO4 ,1400 C
(ethylpropionate) 3) C2 H 5Cl , Mg  dry ether  4) C2 H 2 , dil.H 2 SO4 , HgSO4
10. The IUPAC name of C2 H 5  O  CH  CH 3 2 15. Among the following compounds, the one
which does not react with sodium is
1) Ethoxy propane 2) 1,1-dimethyl ether
3) 2-Ethoxy isopropane 4) 2-Ethoxy propane 1) CH 3CHOHCH3 2) CH 3OCH 3
11. ‘A’ reacts with C2H5I giving ‘B’ and NaI. Here 3) CH 3COOH 4) C2 H5OH
‘A’ and ‘B’ respectively are 16. Which of the following halogen acids is most
1) CH 3COONa, CH 3OCH 3 reactive towards the given reaction ?
2) C2 H 5OC2 H 5 , C2 H 5COOC2 H 5 R  O  R 
HX

1) HCl 2) HI 3) HBr 4) Equally reactive

3) C2 H 5ONa, C2 H 5OC2 H 5
17. Which of the following compounds is pro-
4) C2 H 5OH , C2 H 5OC2 H 5 duced when this reaction takes place ?
12. Which of the following compounds when CH3
heated with CO at 1500C and 500 atm. pres- |
sure in presence of BF3, forms ethyl propi- H3C  C  O  CH 3 
HI
cold

onate ? |
CH3
1) C2 H 5OH 2) CH 3OCH 3
3) C2 H 5OC2 H 5 4) CH 3OC2 H 5 CH 3 H
| |
13. One mole of diethyl ether on heating with 1) H3C  C  OH 2) H  C  OH
conc.HI gives | |
1) 1 Mole of C2 H 5 I and 1 mole of C2 H 5OH CH 3 H
2) 2 Moles of iodoethane 3) Both of these 4) None of these
3) 2 Moles of ethanol 18. Alcohols can be distinguished from ethers by
4) Iodoethane and ethanol but not in a 1:1 mole 1) Sodium metal 2) Ester formation
ratio 3) Iodoform test 4) All the above
14. The major product obtained on the
19. CH 3CH  CH 2  
HCl
 X 
Dry Ag 2O
Heat
 Y The
monobromination (with Br2 / FeBr3 ) of the
product Y in the above sequence is
following compound is 1) Di isopropyl ether 2) Di n - propyl ether
3) 2 - Propanol 4) 1, 2 - Epoxypropane
20. A mixture of ether and ......... gives tempera-
ture as low as 163 K
1) NaCl 2) Ice 3) Solid CO2 4) C2 H5OH
1) Both A and R are true and R is the correct
explanation to A
2) Both A and R are true and R is not the correct
explanation to A
3) A is true but R is false
1) 2) 4) A is false but R is true
21. Assertion (A) : Ethers behave as Lewis base
in the presence of mineral acids.
Reason (R) : Oxygen atom in ether is having
lone pair electrons.
22. Assertion (A) : Diethyl ether is used as general
3) 4) anaesthesia.
Reason (R) : Diethyl ether produces
unconsciousness without effecting lungs.
23. Assertion (A): Ethers are relatively inert 14. Methoxy group is strong ring activating group
when compared to C2 H 5OH the methyl group
Reason (R): The hybridization of C and O in 15. Due to absence of acidic hydrogen ether has no
CH 3  O  CH 3 is SP3 reaction with sodium metal.
24. Assertion(A): Diethyl ether reacts with hot 16. Order of reactivity HI > HBr > HCl
Conc H 2 SO4 and gives ethyl hydrogen 17. Reaction proceeds by SN1 mechanism
sulphate Y  CH 3  CH  O  CH  CH 3
19. X  CH 3  CH  CH 3 ; | |
Reason (R) : The reaction involves cleavage CH 3 CH 3
|
of C-O bond in diethyl ether. Cl
25. Assertion (A): Ethers behave as base in
presence of mineral acids 20. Acts as freezing mixture
Reason (R): Oxygen atom in ether is having
lonepair LEVEL-I (H.W)
26. Assertion (A): Alkyl aryl ethers on reacton with
HI give alkyl iodide, phenols NOMENCLATURE
Reason (R): Aryl - oxygen bond is weaker than 1. The following represents ether
alkyl oxygen bond. 1) (RCO)2 O 2) RCOOR 3) RCOR 4) ROR
2. The dialkyl derivative of H2O is
LEVEL-I (C.W) - KEY 1) Alcohol 2) Ether 3) Ester 4) Ketone
1) 1 2) 2 3) 2 4) 2 5) 3 6) 4 7) 4 3. Which of the following is a simple ether?
8) 3 9) 2 10) 4 11) 3 12) 3 13) 2 14) 4 1) CH3 OCH3 2) CH3OC2H5
15) 2 16) 2 17) 2 18) 4 19) 1 20) 3 21) 1 3) CH3CH2OCH(CH3)2 4) C2H5OC3H7
4. Ethers are isomeric with
22) 1 23) 2 24) 1 25) 1 26) 1
1) Aldehydes 2) Acids
LEVEL-I (C.W) - HINTS 3) Alcohols 4) Ketones
1. Alcohols and ethers are functional group 5. CnH2n+2O is the general formula of ethers. To
isomers. exhibit the functional group isomerism 'n'
must be minimum
2. CH 2  CH 2  O  CH 2  CH 3 ,
1) 1 2) 2 3) 3 4) 4
CH 3  O  CH 2  CH 2  CH 3 and
PREPARATION METHODS
CH 3  O  CH  CH 3 2 6. Heating together sodium ethoxide and ethyl
chloride will give
3. CH 3  CH 2  O  CH 2  CH 3 is ethoxy ethane
1) ether 2) ethyl alcohol
4. C6 H 5OH 
NaOH
C2 H 5Cl
 C6 H 5  O  C2 H 5 3) acetaldehyde 4) acetic acid
7. Williamsons synthesis is used to prepare
5. 2 RX  Ag 2O  ROR  2 AgX 1) Diethyl ether 2) PVC
 
C2 H 5  O  C2 H 5  C2 H 5  O  O  C 2 H 5 3) Bakelite 4) Ethyl alcohol
O
6.
7. In ethers H-bond is absent 8. Which of the following is not an isomer of di-
.. .. ethyl ether ?
8. C2 H 5  O  O  C 2 H 5 1) 2-methyl - 2- propanol 2) 2-Methoxypropane
.. ..
3) 2-Methyl-1-propanol 4) Ethoxyethane
9. 2C2 H 5OH , conc.H 2 SO4 ,1400 C
PROPERTIES AND USES OF ETHERS
10. Nomenclature 9. The compound in which hydrogen bonding
11. C2 H 5ONa, C2 H 5OC2 H 5 is not possible is
12. chemical reactions of ether 1) C6 H 5OCH 3 2) CH3CH2OH
13. C2 H 5  O  C 2 H 5  2HI 2C 2 H 5 I  H 2O 3) H2O 4) CH3COOH
10. Diethyl ether is used as 10. All are uses of diethyl ether.
1) Anaesthetic 2) Solvent 3) Refrigerant 4) All 11. Halothane does not cause side effects.
11. The safest general anaesthesia used at present 12. CF3CHClBr
is
13. methoxypropane
1) chloroform 2)diethyl ether
14. Dry silver oxide
3) acetylene 4) halothane
12. Formula of halothane is 15. C2 H 5 I and H 2O
1) CF2Cl2 2) CF3Cl
16. C6 H 5ONa  C2 H 5 I  C6 HPhenetole
5OC 2 H 5
3) CF3-CHClBr 4) (C2F4)n
13. The IUPAC name of an unsymmetrical ether 17. Alkoxy group is ortho, para directing group
with the molecular formula C4 H10O
1) Ethoxypropane 2) Methoxyethane
3) Ethoxyethane 4) Methoxypropane
14. Consider the following reaction

C2 H 5 I 
X
 (Pleasant smelling liquid), X is
1) Sodium 2) Dry silver oxide
3) Ethyl chloride 4) Dry silver powder

15. C2 H 5  O  C2 H 5  excess
HI  hot   X  Y , here
e
X and Y are
1) C2 H 5 I and C2 H 5OH 2) C2 H 5 I and H 2O
3) C2 H 5OH  H 2O 4) C2 H 4  H 2O
16. Which one of these is formed on heating so-
dium phenoxide with ethyl iodide ?
1) Phenetole 2) Ethyl phenyl alcohol
3) Phenone 4) None of these
17. Anisole with conc. HNO3 and conc. H 2 SO4
gives
1) Phenol 2) Nitrobenzene
3) O- and - P-Nitroanisole 4) O- Nitroanisole
18. Oxygen atom in ether is
1) Very active 2) Replaceable
3) Active 4) Relatively inert
LEVEL-I (H.W) - KEY
1) 4 2) 2 3) 1 4) 3 5) 2 6) 1 7)1
8) 4 9) 1 10) 4 11) 4 12) 3 13) 4 14) 2
15) 2 16) 1 17) 3 18) 4
LEVEL-I (H.W) - HINTS
1. General formula is R-O-R
2. R-O-R is ether
3. Same type of alkyl groups are attached to
oxygen atom.
4. Alcohols are isomeric with ethers
5. Two
6. C2 H 5Cl  C2 H 5ONa  C2 H 5OC2 H 5  NaCl
7. Ethers
9. In ethers H-bond is absent
 ETHERS A  B  CH 3  O  C  CH 3 2 
9. HI
 X Y .
Correct statement among the following is
1) A and B are CH3ONa and (CH3)3CBr
LEVEL-II (C.W) 2) X and Y are CH3I and (CH3)3COH
3) X and Y are CH3OH and (CH3)3CI
METHODS OF PREPARATION 4) A and B are CH3OH and (CH3)3COH
1. Which of the following pairs of reagents will
not form ether 10. P  Q  Anisole  HI
 R  S.
1) C2H5Br + C2H5ONa 2) C2H5Br + CH3ONa Correct statement among the following is
1) P and Q are C6H5ONa and C2H5Cl
3) CH3Br + C2H5ONa 4) C2H5Br + HCOONa 2) R and S are C6H5I and CH3OH
2. What is Y in the following reactions 3) R and S are C6H5OH and CH3I
C2 H 5 I  NaOC2 H 5  X  NaI 4) P and Q are C6H5Cl and CH3ONa
X  2 HI  2Y  H 2O 11.  CH 3 3 COCH 3 
 HI
  CH 3 3 CI  CH 3OH
1) C2 H 6 2) C2 H 5 I 3) C2 H 4 4) C2 H 5OC2 H 5 It follows which mechanism ?
3. Which of the following cannot be prepared 1) SN1 2) SN2 3) E1 4) E2
by using Williamson synthesis ? 12. Which of the following reagents can distin-
1) Methoxybenzene 2) Benzyl-p-nitrophenol ether guish ethyl methyl ether from isopropyl al-
3) Methyl tert-butyl ether 4) Ditertiary butyl ether cohol ?
4. Methoxy benzene is called anisole. 1) Br2CCl4 2) AgNO3 / NH 4 OH 
3) I 2 and NaOH 4) CuCl / NH 4OH 
How many more structures can be 13. Which of the following compounds is pro-
drawn for the same formula ? duced with this reaction takes place ?
C6 H5  O  CH 2 C6 H5 
HI
cold
1) 5 2) 4 3) 3 4) 2
5. Which of the following types of ethers can-
not be synthesized by Williamson synthesis?
CH 3 CH 3 CH 3 CH 3 1) 2)
| | | |
1) H 3C  C  O C  CH 3 2) H 3C  C  O C  H
| | | | 3) Both of these 4) None of these
CH 3 CH 3 CH 3 CH 3
14. Which of the following compounds is pro-
3) C6 H5  O  C6 H 5 4) None of these duced when this reaction takes place ?
6. Which alkyl halide would be preferred for CH 3  CH  OCH 3 
HI
cold
the synthesis of the following ether by |
Williamson synthesis ? CH 3
CH 3
CH 3
|
1) | 2) CH3  OH
H5C2  O  C  H
|
CH 3  CH  OH
CH 3 3) Both of these 4) None of these
1) n-Propyl chloride 2) Isopropyl chloride LEVEL-II (C.W) - KEY
3) Ethyl chloride 4) Methyl chloride
1) 4 2) 2 3) 4 4) 2 5) 4 6) 3 7) 1
PROPERTIES AND USES OF
ETHERS 8) 4 9) 3 10) 3 11) 1 12) 3 13) 2 14) 1
7. Which of the following does not react with LEVEL-II (C.W) - HINTS
diethyl ether 1. C2 H 5 Br  HCOONa
1) C2H5ONa 2) AlCl3 3) BF3 4) HCl 
2. (C2 H 5 )2 O  2 HI   2C2 H 5 I  H 2O
8. C O C bond in ethers can be cleaved by
3. Tertiary alkyl halides do not gives ethers.
1) KMnO4 2) LiAlH 4 3) KOH 4) HI 5. Williamson’s synthesis follows SN2 mechanism
6. Williamson’s synthesis follows SN2 mechanism 2)  CH3 3 C  I and CH 3CH 2OH
7. C2 H 5ONa
3)  CH3 3 C  I and CH3CH 2 I
8. HI 4) C  H3C 3  O   CH 2CH3I 
9. X and Y are CH3OH and (CH3)3CI |
10. R and S are C6H5OH and CH3I H
11. S N1
8. CH 3  CH  OCH 3 HI
excess, 

12. Ethers do not gives Iodo form test |
13. Phenoxide ion is stabilized by resonance CH 3
14. Nucleophile attacks on less hindered carbon Which of the following is not formed in the
above reaction ?
1) Methyl iodide 2) Isopropyl iodide
3) Isopropyl alcohol 4) All of these
METHODS OF PREPARATION 9. C 6 H 5  O  CH 2 CH 3  HI
 which of the fol-
1. The reaction, sodium alkoxide + alkyl halide lowing is not formed in this reaction ?
 ether is called 1) C6 H 5  I 2) C6 H5  OH
1) Wurtz reaction 2) Kolbe’s reaction 3) Both of these 4) None of these
3) Williamson’s synthesis 4) Perkin’s reaction 10. Ethyl LEVEL-II (H.W)
phenyl ether on reaction with excess
2. In which of the following reactions, the HI yields
product is an ether? 1) Ethyl iodide and iodobenzene
2) Ethyl iodide and phenol
1) C6 H 6  CH3COCl / anhydrous AlCl3
3) Ethyl alcohol and phenol
2) C2 H5Cl  aq.KOH 4) Ethyl alcohol and iodobezene
3) C6 H 6  C6 H5COCl / anhydrousAlCl3
LEVEL-II (H.W) - KEY
4) C2 H5Cl  C2 H5ONa 1) 3 2) 4 3) 4 4) 2 5) 3 6) 3 7) 2
3. Williamson’s synthesis is an example of
8) 3 9) 1 10) 2
1) Nucleophillic addition
2) Electrophillic addition LEVEL-II (H.W) - HINTS
3) Electrophillic substitution 1. Williamson’s synthesis
4) Nucleophillic substitution reaction 2. C2 H 5Cl  C2 H 5ONa  Nacl  (C2 H 5 )2 O
4. Ethoxy benzene is called PHENETOLE. 3. Nucleophillic substitution reaction
5.  C2 H 5 2 O  HI  C2 H 5 I  C2 H 5OH
How many more ethers can be 6. sp3 hybridisation
7. Nucleophile attacks on tertiary carbonium ion
drawn for the same formula ?
which proceeds by SN1 mechanism
HI
1) 5 2) 4 3) 3 4) 2 8. CH 3  CH  O  CH 3   CH 3  I  CH 3  CH  OH
| |
PROPERTIES AND USES OF ETHERS CH 3 CH 3
5. Diethyl ether reacts with cold. HI to give HI
1) Ethyl iodide 2) Ethyl alcohol CH 3  CH  I
|
3) Both 1 and 2 4) Ethylene CH 3
6. Hybridisation of oxygen in diethyl ether is HI
9. C6 H 5  O  C6 H 5   C6 H 5OH  C 2 H 5 I
1) sp 2) sp 2 3) sp3 4) sp 3 d
10. In phenol C - O bond not cleaved by HI
7. In the reaction
heat
 CH3 3 C  O  CH 2CH3  (1HI
mole)
 the
1. A compound X of the formula C2H6O, on
product(s) formed is (are) reaction with Na metal gave Y, X also reacts
1)  CH3 3 C  OH and CH3CH 2 I with PCl5 to give Z. The product obtained in
the reaction between Y and Z is
 4)  CH 3CH 2 2 O
1) CH3CHO 2) CH3COCH3
3) Both (1) & (2)
LEVEL-III
3) CH3COOC2H5 4) C2H5OC2H5
2. AlCl
CH2=CH2 + Hl  3 A 
Aq . KOH
 B 12. C2 H5  O  C2 H5  HI excess 

conc. H 2 SO4
1400 C
C, 'C' is 1) C2 H5OH and C2 H 5 I 2) 2 moles of C2 H 5 I
1)Ethoxy ethane 2) Ethanol 3) 2 moles of C2 H5OH 4) C2 H 4
3) Ethanal 4)Acetone
13. C6 H5  O  CH3  HI excess  
CH3-CH2 Cl   A   B
Aq . KOH conc. H 2 SO4
3. 1400 C
1) CH 3OH and C6 H 5 I 2) CH 3 I and C6 H5OH

Al2 O3
3600 C
 C. Then ‘C’ is
1) Ethyne 2) Ethene 3) CH 3 I and C6 H 5 I 4) C6 H 6 and CH 4
3) Ethoxy ethane 4) Ethyl alcohol
4. In the sequence of reactions (A) is : LEVEL-III - KEY
(A)  (B) 
Na 2 5
 (C) 
 C2H5I
C H I / heat HI / heat 1) 4 2) 1 3) 2 4) 3 5) 1 6) 1 7) 3
1) Acetic acid 2) Methyl alcohol 8) 1 9) 1 10) 3 11) 1 12) 2 13) 2
3) Ethyl alcohol 4) Propionic acid
LEVEL-III - HINTS
5. HBr reacts with CH 2  CH  OCH 3 under
anhydrous conditions at room temperature 1. X  C2 H 5OH , Y  C2 H 5ONa; Z  C2 H 5Cl
to give 2. A  C2 H 5 I , B  C2 H 5OH , C  C2 H 5OC2 H 5
1) H 3C  CHBr  OCH 3 2) CH 3CHO and CH 3 Br 3. A  C2 H 5OH , B  C2 H 5OC2 H 5 , C  C2 H 4
3) BrCH 2 CHO and CH 3OH 4) BrCH 2  CH 2  OCH 3
4. A  C2 H 5OH , B  C2 H 5ONa, C  C2 H 5OC2 H 5
6. The major product obtained when tert-butyl
6. It proceeds by elemination instead of
bromide is heated with sodium ethoxide is
1) 2 - Methyl - 1 - propene 2) Ehene nucleophillic substitution reaction.
3) tert - Butyl methyl ether 4) Diethyl ether CH 3 Br  NaOC  CH 3 3  CH 3  O  C  CH 3 3
7. A  B  CH 3  OC  CH 3 3 
HI

X Y .  HI
Correct statement among the following is 7. CH 3  OH   CH 3 3 C  I
1) A and B are CH 3ONa and  CH 3 3 CBr 11. A  CH 3CH 2CH 2 Br ; B  CH 3CH 2CH 2ONa
2) X and Y are CH 3 I and  CH 3 3 COH C   CH 3CH 2CH 2 2 O
3) X and Y are CH 3 OH and  CH 3 3 CI 12.

4) A and B are CH 3 OH and  CH 3 3 COH C2 H 5  O  C2 H 5  HI  excess 

8. IUPAC name of methyl isopropyl ether is 
1) 2-methoxy propane 2) 3-methoxy propane C2 H 5 I  C2 H 5OH
3) Ethoxy ethane 4) Methoxy ethane
 HI
9.  CH 3 3 COCH 3 
 HI
  CH 3 3 CI  CH 3 OH It
follows which mechanism? C2 H 5 I
1) S N 1 2) S N 2 3) E1 4) E2 C6 H 5OCH 3  HI  CH 3 I  C6 H 5OH
10. Which of the following is strongest Lewis  HI
Base 13.
No reaction
1) H 2 O 2) CH 3OH 3) CH 3OCH 3 4) C6 H5OH
11. CH 3CH 2 CH 2 OH  PBr3  A ,
CH 3CH 2 CH 2 OH  Na  B , A  B  C . 1. Which of the follwoing ether cannot be
Product ‘C’ is prepared by Williamson’s synthesis
1)  CH 3CH 2CH 2 2 O 2) CH 3  CH  CH 2
 O
O LEVEL-IV
1) 2)
CH2 = CH CH = CH2

3) 4) All
2. 1.68 mg of an organic compound (A) with
molecular formula  C9 H12O3  on Zeisel
estimation produces an yellow precipitate of
wt 4.7 mg the compound (A) is

1) 2)

3) 4)

O
 HBr

aq

3.

 Cs 2   B  halogen compound 

HBr

A & B respectively are

1) CH 3  Br , CH 3  Br 2) CH 3  Br ,

3) , CH 3  Br 4)

LEVEL-IV - KEY : 1) 3 2) 3 3) 1
LEVEL-IV - HINTS
4.7 103
2. Number of moles of AgI=  2  105
235
1.68 103 grams of given compound forms
5
2  10 moles of AgI
Number of moles of AgI given by 168 grams of
168  2  105
given compound is 2
1.68 103
Number of moles of AgI is equal to number of
moles of alkoxy groups in 1 mole of ether
 PHENOLS
Nomenclature
SYNOPSIS
Common IUPAC
Molecule name name
 Aromatic hydroxy compounds in which -OH
OH
group is bonded to benzene ring directly are
called phenols. Monohydroxy benzene is called Phenol Phenol
phenol. Phenol is also known as carbolic acid.
 Phenols are classified as monohydroxy,
OH
dihydroxy and trihydroxy compounds
CH3 2-methyl
OH OH OH o-cresol
Phenol
OH OH OH
OH

3-methyl
m-cresol
Phenol
monohydric dihydric trihydric CH3
 The simplest hydroxyl derivative of benzene is OH
phenol which is also its accepted IUPAC name.
4-methyl
 The hydroxyl derivatives of toluene are o–, m– p-cresol
Phenol
and p– cresol.
CH3
OH OH OH
OH
CH3 OH
Catechol Benzene-1,
2-diol

CH3 OH
CH3
Benzene-1,
o-cersol m-cersol p-cersol Resorcinol
3-diol
 Dihydroxy derivatives of benzene are called OH
benzene diols. OH
OH OH OH
OH Hydroquinol Benzene-1,
4-diol

OH
OH OH
HO OH
OH (Benzene 1,2,
Pyrogallol 3-triol)
Catechol Resorcinol Hydroquinol

 In phenols, the –OH group is attached to sp 2 OH

hybridized carbon of an aromatic ring. (Benzene 1,2,
Phloroglucinol
 The bond angle of C–O–H in phenol is 1090. 5-triol)
The carbon-oxygen bond length is 136 pm HO OH
OH
which is slightly less than that in methanol. This
H 3C CH3
is due to partial double bond character on 2,6-dimethyl
account of conjugation of unshared electronpair Phenol
of oxygen with the aromatic ring.
Methods of preparation: Phenol was first Physical properties: Phenol has higher
isolated from coaltar. boiling point than the arenes or haloarenes or
From Haloarenes: ethers of same molecular weight. It is due to the
formation of intermolecular hydrogen bond.
X  Compared relative to pure aromatic
hydrocarbons phenols are more soluble in water
 NaOH 350 C & 300 atm due to their ability to form hydrogen bonding
with water.
O Na OH  As the hydrocarbon part increases in size and
mass, the solubility decreases due to increasing
HCl of hydrophobic nature.
Chemical properties:
Acidic nature of phenol: Alcohols and
From Diazonium salt: phenols react with active metals like Na, K, Al
NH2

N2Cl
 etc to liberate hydrogen gas.
2ROH  2 Na  2RONa  H 2
 NaNO2  HCl 05 C 2 C6 H 5OH  2 Na  2C6 H 5ONa  H 2
OH  Phenols also react with aqueous NaOH solution
to produce the salt sodium phenoxide and water.
H2O2 warm N2  HCl
C6 H 5OH  NaOH  C6 H 5ONa  H 2O
 The acidic nature of alcohols is due to the polar
nature of O-H group.
From Benzene Sulphonic acid:  Electron releasing groups like alkyl groups
SO3H increase the electron density on oxygen and
decrease the polarity of O-H bond. This
conc.H2SO4,SO3 moltenNaOH decreases the acidic strength.
 Even though the electron releasing groups like
 CH 3 ,C 2 H 5 etc decrease the acidic strength
 
O Na O

HCl
of phenol, Phenol does not liberate CO2 with
 NaCl
Na 2CO 3 or NaHCO3 because phenol is weakly
From cumene:Phenol is manufactured from acidic than carbonic acid and carboxylic acids.
cumene (isopropyl benzene) Note: Acids stronger than carbonic acid, decomposes
CH3
Na2CO3 and NaHCO3 solutions liberating
CH(CH3)2 H3CCOOH
CO2 with brisk effervescence.
Relative acid strength: Carboxylic acid >
O2 (oxidation with air) Carbonic acid > Phenol > Methyl alcohol >
Water > Other alcohols
cumene hydroperoxide  The reactions of phenol with metals as well as
OH NaOH indicate that phenol is relatively more
acidic than alcohols and also water.


H / H2O C3COCH3 This is explained on the basis of the structure of
phenol.
 The hydroxyl group in phenol is directly pKa Values of some Phenols and Ethanol
attached to sp2 carbon of benzene ring. The sp2 Compound Formula pKa
carbon attached to ‘O’ being more
electronegative than sp3 carbon of alcohols, it o - Nitrophenol o  O2 N  C6 H 4  OH 7.2
decreases the electron density on oxygen.
m - Nitrophenol m  O2 N  C6 H 4  OH 8.3
Because of this oxygen develops still more
electron seeking character and releases proton p - Nitrophenol p  O2 N  C6 H 4  OH 7.1
by taking the shared pair of electrons with it.
 The acidic nature of phenol can also be Phenol C6 H 5  OH 10.0
explained on the basis of resonance stabilization
of phenoxide ion. o -Cresol o  CH 3  C6 H 4  OH 10.2
 Electron withdrawing groups present at ortho
m -Cresol m  CH 3C6 H 4  OH 10.1
and para positions (but not at meta) increases
the acidic nature of phenol. Gretaer the number p -Cresol p  CH 3  C6 H 4  OH 10.2
of such groups at ortho and para positions higher
is the acidic nature of phenol. Ethanol C2H5OH 15.9
 Electron releasing group present at ortho and
para positions (but not at meta) decreases the W.E-1: O - Nitro phenol is less acidic than
acidity of phenols. Greater the number of such P - nitro phenol. Give reason
groups at ortho and para positions lesser is the Sol. O - nitro phenol exist in intramolecular hydrogen
acidic nature of that phenol. bonds. So acidic nature is less.
 Acidic strength increases with the decrease of
the pK a values. Esterification of Phenol: Phenols react
 Order of acidic strength of phenols is as follows with carboxylic acids and their derivatives like
acid chlorides and anhydrides to form esters.
OH OH OH
This reaction is called Schotten-Baumann
O2N NO2
reaction.
> >
C6 H 5OH  RCOOH 
 C6 H 5  O  CO  R  H 2O
O2N NO2  During esteification H comes from phenol
NO2
3,5-dinitro
NO2 and ‘OH’ comes from carboxylic acid.
Picric acid phenol p-nitro
phenol C6 H 5OH  RCOCl 
pyridine

OH OH OH C6 H 5  O  CO  R  HCl
NO2
 Salicylic acid on acetylation gives acetyl
> > salicylic acid known as Aspirin.
COOH COOH
NO2
o-nitro m-nitro phenol OH OCOCH3
phenol phenol conc.H2SO4
 (CH3CO)2O
OH OH OH
CH3 acetyl salicylic
acid (aspirin)
> >
Electrophilic aromatic substitution
CH3 reactions of phenol:In phenol, -OH group
o-cresol CH3 o-cresol is ring activating and ortho and para directing
p-cresol as these positions get more electron density
 The greater the pKa value, the weaker the acid. through resonance.
 Nitration  When the reaction is carried out in solvents of
OH OH OH low polarity such as CHCl3 or CS2 and at low
NO2 temperature, monobromophenols are formed.
dil.HNO3
  Here no Lewis acids like FeBr3 are required
because highly activating effect of -OH group
O - nitrophenol polarises bromine quickly.
NO2
P - nitrophenol  Phenol reacts with bromine water and gives
1) Intramolecular 1) Intramolecular 2,4,6-tribromo phenol (white precipitate)
H bond H bond
2) Steam volatile 2) Less volatile
 In water phenol forms phenoxide ion which
activates the benzene ring.
 Nitration of phenol is gives a poor yield OH OH
because nitric acid also causes oxidation of Br Br
phenol. H 2O
Alternate method of nitration:- 3Br2
0-5C

Br
Reimer-Tiemann reaction: Phenol when
treated with chloroform in the presence of NaOH
gives salicylaldehyde.
Mechanism:
i) CHCl3  OH   H 2O  CCl3 : CCl2  Cl 
Dichloro carbene ( : CCl2 ) is the attacking
electrophile in this reaction :
 Phenol when treated with conc. HNO3 gives
2,4,6-trinitrophenol known as picric acid O O
OH OH H
O2N NO2
: CCl2
conc.HNO3 CCl2

O O OH
CHCl2 CH(OH)2 CHO
NO2 ii) 
NaOH H
 The yield in the reaction is poor. Now a days
picric acid is prepared by treating phenol with
conc. H 2SO 4 and then with conc. HNO3 . Salicylaldehyde

OH OH
SO3H
OH
 If CCl4 / KOH is used salicylic acid will be
O2N NO2

conc.H2SO4 conc.HNO3 formed

OH OH
CHCl2 COOH
SO3H NO2 CCl4, KOH, 
Picric acid

Halogenation:- H / H2O
OH OH OH Salicylic acid
Br
Br2 in CS2 at 0C
Kolbe’s reaction: Phenoxide ion generated
 by treating phenol with sodium hydroxide is
even more reactive than phenol towards
Br electrophilic aromatic substitution.
 Uses of Phenol: It is a raw material for the
OH ONa manufacture of important dyes, drugs and
pharmaceuticals.
NaOH O=C=O
 2,4-dichloro-3,5 dimethyl phenol is used as
powerful antiseptic under the name Dettol.
ONa OH  It is used in the manufacture of drugs like
COO COOH Aspirin, Salol etc.
H  0.2% aqueous Phenol is used as an antiseptic.
H
 Phenol on reaction with urea and formal dehyde
(major) gives condensation regin (PVF) used as wood
2-hydroxy benzoic acid adhesives.
(Salicylic acid)
Tests of Phenol:
 If KOH is used parahydroxy benzoic acid will i) Phenol in water gives violet colour with a drop
be formed as major product. of FeCl3 .
Action of Zinc dust:Phenol on heating ii) Phenol in water gives white precipitate with
with zinc dust produces benzene. bromine water.
OH iii) Phenol gives blue colour indophenol with
ammonia and sodium hypochlorite.
 Zn  ZnO W.E-2:Give equations of the following reactions:
(i) Reaction of propene with mercuric acetate
Oxidation: Phenol on oxidation with chromic followed by hydrolysis.
acid ( Na 2Cr2O7  H 2SO 4 ) produces benzoquinone, (ii) Oxidation of propan-1-ol with alkaline
which is a conjugate diketone. In the presence KMnO4 solution
of air, phenols are slowly oxidised to dark (iii) Reaction of bromine in CS2 with phenol
coloured mixtures containing quinones. (iv) Action of dilute HNO3 with phenol
OH O Sol. (i) CH3  CH  CH 2 + Hg(OAc)2 + H2O 

propene

 CH3  CH  CH3
NaBH 4
chromic acid CH3  CH  CH 2 
H2CrO4 | | |
OH HgO OH
O (ii) CH3 – CH2 – CH2OH + 2[O]   CH3
Alk. KMnO 4
benzoquinone 
– CH2 – COOH + H2O
Fries rearrangement:
OH OCOCH3 OH OH OH
Br
anhydrous AlCl3 Br4
 (CH3CO)2O  OH OH
(in CS2)
(iii)
dil.)
OH OH Br (Major)
COCH3 (Major)
AlCl3 NO
OH OH
 OH
Rearrangement NO2

O-hydroxy dil.)  H2O

acetophenone COCH3 (iv)
P-hydroxy
acetophenone NO2
OH
NO2

H2O
W.E-3:You are given benzene, conc. H2SO4 and 7. Phenol is
NaOH. Write equations for the preparation of 1. a base weaker than ammonia
phenol using these reagents. 2. an acid stronger than carbonic acid
SO 3H 3. an acid weaker than carbonic acid
4. a neutral compound
H 2SO 4 (conc.) 8. Phenol reacts with bromine in carbon
  disulphide at low temperature to give
SO 3Na 1. m-bromophenol
2. o- and p-bromophenol
NaOH
 
3. p-bromophenol 4. 2,4,6-tribromophenol
9. Phenol is less acidic than
ONa
1. p-nitrophenol 2. ethanol
 fusion 3. cresol 4. benzyl alcohol
Sol. Na 2SO 3
 2NaO  10. Phenol on treatment with conc. HNO3 gives
OH 1. picric acid 2. o-and m-nitrophenols
3. cresol 4. resorcinol
dil. HCl
H 2O
NaCl LEVEL-I (C.W) - KEY
1) 3 2) 3 3) 1 4) 4 5) 1 6) 4 7) 3
LEVEL-I (C.W) 8) 2 9) 1 10) 1

METHODS OF PREPARATION LEVEL-I (C.W) - HINTS

1. Phenol is also called 1. Phenol also known as carbolic acid
1. salicylic acid 2. benzyl alcohol
OH
3. carbolic acid 4. salol
2. Benzene diazonium chloride on hydrolysis 2. +
C6H5N2Cl  
2 H O
gives warm + N2 + HCl
1. Benzene 2. Benzyl alcohol
3. Phenol 4. Chlorobenzene 3. Picric acid
NOMENCLATURE OH OH
3. Which does not have a carboxyl group? Br Br
1. Picric acid 2. Ethanoic acid + 3Br2 
3. Aspirin 4. Benzoic acid 4.
PROPERTIES
Br
4. When phenol is treated with excess of
bromine water, it gives 5. Sodium bicarbonate
1. m-bromophenol 2. o- and p-bromophenol 6. It is Reimer Tiemann reaction
3. 2,4-dibromophenol 4. 2,4,6-tribromophenol 7. PKa of phenol = 10
5. Phenols does not react with PKa of carbonic acid is less than 10
1. sodium bicarbonate 2. sodium hydroxide
OH OH OH
3. potassium hydroxide 4. ferric chloride Br
i ) CHCl / NaOH
   3   Br in CS
6. Phenol ii ) H 
Salicylaldehyde. This 
2 2 +
8.
reaction is known as
1. Gattermann aldehyde synthesis Br
2. Sandmeyer’s reaction 9. PKa of phenol is 10
3. Perkin’s reaction 4. Reimer-Tiemann reaction 10. Picric acid
 9. Br2 dissolved in CS2 reacts with phenol at
LEVEL-I (H.W) 273K to give ..... as the major product
1) o - Bromophenol 2) m - Bromophenol
METHODS OF PREPARATION 3) p - Bromophenol 4) 2,4,6-Tribromophenol

1. Cumene  i ) O2
ii ) H O/ H
(X) and (Y) LEVEL-I (H.W) - KEY
2

(X) and (Y) respectively are 1) 3 2) 3 3) 2 4) 2 5) 2 6) 2 7) 2

1. toluene, propene 2. toluene, propylchloride 8) 4 9) 3
3. phenol, acetone 4. phenol, acetaldehyde
2. NaNO  HCl / O C
In the reaction C6 H 5 NH 2  LEVEL-I (H.W) - HINTS
X
o
2

CH3 CH3

H2O, warm
Y . ‘Y’ is
H3C – CH H3C – C – O – OH OH
1) C6 H 5Cl 2) C6 H 6 3) C6 H 5OH 4) C 6 H 5CHO

O

2 
H O
H
+ CH3COCH3
NOMENCLATURE 1. 2

3. Picric acid is a yellow coloured compound. X Y

Its chemical name is phenol acetone
1. m-nitrobenzoic acid 2. 2,4,6-trinitrophenol +

3. trinitrotoluene 4. trinitroaniline
PROPERTIES NaNO2  HCl
  H O

warm 
2. 0 5C
2

4 C6 H 5OH  CHCl3  NaOH salicylaldehyde

The electrophile involved in the above
3. 2, 4, 6 - trinitro phenol
reaction is.
 4. H 2O  CCl3  : CCl2  Cl 
1. dichloromethyl cation (C HCl2 )
electrophile (dichloro carbene)
2. dichlorocarbene (: CCl 2 ) 6. phenols are acidic in nature
3. trichloromethyl anion (CCl3 ) 7. cresols are less acidic than phenol

8. Kolbe’s reaction
4. formyl cation (C HO) 9. monobromo phenols are formed
5. The reaction,
C6 H 5ONa  CO2  H 2O  C6 H 5OH  NaHCO3
suggest that
1) Phenol is a stronger acid than carbonic acid
2) Carbonic acid is a stronger acid than phenol
3) Water is stronger acid than phenol
4) None of the above
6. Which of the following compounds when
dissolved in water, gives a solution with pH
less than seven ?
1) CH 3COCH 3 2) C6 H 5OH 3) C6 H 5 NH 2 4) C2 H 5OH
7. Increasing pKa values of o-, m- and p- cresols is
1) o<p<m 2) m<p=o 3) m<o<p 4) p<o< m
8. Identify the product Z in the following
sequence of reactions

phenol 
NaOH
 X  CO2
4  7 atm ,410 K
 Y 
H 3O
Z
1) Aspirin 2) Salicyladehyde
3) Benzoic acid 4) Salicylic acid
 P-nitrophenol
2) 4-Hydroxybenzene-1,3-disulphonic acid,
picric acid
3) 4-Hydroxybenzene-1,3-disulphonic acid,
PHENOLS 2,4-dinitrophenol
4) 3-Hydroxybenzene sulphonic acid, picric acid
LEVEL-II (C.W) 9. Phenol 
NaOH
 A 
1) CO2
2) H 
 B 
( CH 3CO ) 2 O
H
C
Incorrect statement among the following is
1) Preparation of ‘B’ from phenol is called
PROPERTIES OF PHENOL Kolbe’s reaction
1. Phenol (1 mole) reacts with bromine water 2) ‘B’ is steam volatile
to give sym.tribromophenol. The amount of 3) ‘C’ has a free -OH group of ‘B’
bromine required is 4) ‘C’ can be used as antiiflammatory, analgesic
1. 3.0 mole 2. 1.5 mole 3. 4.5 mole 4. 6.0 mole and antipyretic.
2. The most acidic compound among the
following is LEVEL-II (C.W) - KEY
1 phenol 2. ethanol 1) 1 2) 3 3) 2 4) 1 5) 4 6) 4 7) 2
3. 3,5-dinitrophenol 4.4-methoxy phenol
8) 2 9) 3
3. Which one of the following compounds would
undergo nitration with greatest ease LEVEL-II (C.W) - HINTS
1. benzene 2. phenol 1. Phenol required 3 moles of bromine
3. nitrobenzene 4. benzoic acid 2. If – NO2 is present on the benzene ring of
4. Phenol on distilling with zinc dust gives phenols acidic strength increases particularly
1. benzene 2. diphenyl ether when that group is at ortho (or) para positions.
3. diphenol 4. zinc phenoxide 3. PKa of phenol is 10
5. Salicylic acid is produced when phenol in
alcoholic KOH is treated with 4. C6 H5OH 
Zn

C6 H6  ZnO
1. CH 3Cl 2. CHCl3 3. CH 2Cl2 4. CCl4
6. In the fololwing compounds, the decreasing
order of acidity is  CCl4 
KOH

+3NaOH
–NaCl

5.

H O
1. I > IV > III > II 2. II > IV > I > II 
2
HCl
3. II > I > III > IV 4. IV > III > I > II
7. Which order is correct about acidity 6. The correct order of acidity IV > III > I > II
1. CH 3COOH  C6 H 5COOH  C6 H 5OH 7. The correct order of acidity
2. C6 H 5COOH  CH 3COOH  C6 H 5OH C6 H 5COOH  CH 3COOH  C6 H 5OH
3. C6 H 5OH  C6 H 5COOH  CH 3COOH
4. C6 H 5OH  CH 3COOH  C6 H 5COOH
8. Phenol 
conc . H SO
2 4
A 
conc . HNO
3
 B Here A and B 8. A is
are respectively.
1) P-Hydroxy benzenesulphonic acid,
9. ‘B’ is salicyclic acid one that would react fastest with conc. HCl and
anhydrous ZnCl2 is
1) 1-Butanol 2) 2-Butanol
3) 2-Methylpropan-2-ol 4)2-Methylpropanol-1
1. One mole of aniline warmed with the mixture LEVEL-II (H.W) - KEY
of NaNO2  HCl . If we assume 100% yield, 1) 2 2) 4 3) 3 4) 3 5) 2 6) 2 7) 4 8) 4 9) 3
volume of N 2 gas liberated at S.T.P is LEVEL-II (H.W) - HINTS
1) 11.2L 2) 22.4 L 3) 33.6 L 4) 44.8 L 1. 22.4 L
2. Phenol reacts with which one of the following 2. Conjugate diketone is known as benzoquinone.
reagents gives a conjugate diketone will be 3. acetylation
formed ? 4. picric acid
1) Na2Cr2O7 2) conc.HNO3 5. presence of electron with drawing group at o-
and p- positions
3) Zn,  4) Na2Cr2O7  H 2 SO4 6. 22.4 L
3. The reaction, 7. CO2, CO2
C6 H 5OH 
CH 3COCl
Pyridine
 C6 H 5OCOCH 3 8. tertiary alcohol
is called PREVIOUS EAMCET QUESTIONS
1) Reimer-Tiemann reaction 1. The conversion of O -acylated phenol in
2) Schotten-Baumann reaction presence of AlCl3 to P - acylated phenol is an
3) Acetylation 4) Benzoylation example for this type of organic reaction.
4. Which of the following is most acidic ? 1) Addition reaction 2) Substituion reaction
1) Phenol 2) CH 3CH 2OH 3)Molecular rearrangement 4)Elimination reaction
3) Picric acid 4) p-Nitrophenol PREVIOUS EAMCET - KEY: 1) 3
5. The descending order of k b values of the
following compounds is LEVEL-II (H.W)

PROPERTIES OF PHENOL
a) b) c) d) 1. Benzenediazonium chloride on reacting with
phenol in weakly basic medium gives
1. benzene 2. chlorobenzene
1) d > b > c > a 2) a > c > b > d 3. diphenyl ether 4. p-hydroxy azobenzene
3) b > d > c > a 4) a > c > d >b 2. The reaction
6. One mole of aniline warmed with the mixture
of NaNO2  HCl . If we assume 100% yield,
+ ClCOC6H5  is known as
volume of N2 gas liberated at S.T.P is
1) 11.2L 2) 22.4L 3) 33.6L 4) 44.8L
1. Wurtz reaction 2. Kolbe reaction
7. When benzene sulphonic acid and p-
3. Rimer-Tiemann reaction
nitrophenol are treated with NaHCO3, the
4. Schotten-Baumann reaction
gases released respectively are
3. Phenol is
1) SO2 , NO2 2) SO2 , NO 3) SO2 , CO2 4) CO2 , CO2 1. a neutral compound
8. Phenol is heated with a solution of mixture 2. a base weaker than ammonia
of KBr and KBrO 3. The major product 3. an acid stronger than carbonic acid
obtained in the above reaction is : 4. an acid weaker than carbonic acid
1) 2-Bromophenol 2) 3-Bromophenol Phenol  Zn
 A 
conc.HNO3
 B 
Zn
C
4. distillation conc.H SO at 600C NaOH
3) 4-Bromophenol 4) 2,4,6-Tribromophenol 2 4

9. From amongest the following alcohols, the In the above reaction, compounds (A), (B)
 and (C) are respectively
1. benzene, nitrobenzene and hydrazobenzene LEVEL-III
2. benzene, nitrobenzene and aniline
3. benzene, dinitrobenzene and m-nitroaniline
1. When phenol reacts with chloroform and an
4. toulene, m-nitrobenzene and m-toulidine
alkali, the compounds formed is
5. Sodium phenoxide when heated with CO2
salicylaldehyde. If pyrene is used in place of
under pressure at 1250 C gives chloroform, the product obtained is
1. salol 2. salicylaldehyde 1. Salicylic acid 2. Salicylaldehyde
3. sodium benzoate 4. sodium salicylate
3. Phenolphthalein 4. Cyclo hexanol
6. Salol prepared from (internal antiseptic)
1. salicylic acid and methyl alcohol 2. The most suitable method of separation of
2. salicylic acid and phenol equal (1:1) mixture of o-and p-nitrophenols is
3. both 1 and 2 4. asprin and phenol 1. Crystallisation 2. Distillation
3. Sublimation 4. Chromatography
LEVEL-III - KEY
1) 4 2) 4 3) 4 4) 1 5) 4 6) 2 1. Both A and R are correct and R is correct
explanation of A
LEVEL-III - HINTS 2. Both A and R are correct but R is not the
__

1. C6 H 5 N 2Cl  C6 H 5OH 

OH
C6 H 5  N  N  C6 H 5  OH correct explanation of A
2. Schotten - Baumann reaction 3. A is correct but R is in correct
3. Phenol is a weaker acid then carbonic acid. 4. A is in correct but R is correct
4. A  C6 H 6 , B  C6 H 5 NO2 C=Hydrazobenzene 3. Assertion (A): o-phenol sulphonic acid on
heating at 1000 C changes to p-phenol
sulphonic acid.
5. + CO2
Reson (R): Sulphonation of phenol is a
reversible process.
6. Salol is obtained form salicylic acid and phenol. 4. Assertion (A) : Phenol and benzoic acid can be
PREVIOUS MAIN QUESTIONS distinguished by NaOH.
1. Sodium phenoxide when heated with CO2 under Reson (R): Benzoic acid is stronger acid than
phenol
pressure at 1250 C yields a product which on 5. Asseriton (A): Phenol is more reactive than
acetylation produces C. benzene towards electrophilic substitution.
Reson (R): In the case of Phenol, the
125C  intermediate Carbocation is more resonance
 CO2 
5atm  B 
AC2O  C
H . stabilized.
6. Assertion (A): p-Nitrophenol is stronger acid
The major product C would be than o-nitrophenol
Reson (R) Intramolecular hydrogen bonding
makes ortho - isomer weaker acid than para
1) 2) - isomer.
7. Assertion (A) : Phenol is more reactive than
benzene towards electrophilic reactions.
Reason (R) : The +R effect of OH group
increases the electron density on benzene
nucleus.
3) 4) 8. Assertion ( A) : Phenols are more acidic than
aliphatic alcohols.
Reason (R) : Phenoxides are stabilized by
resonance.
PREVIOUS MAIN - KEY : 1) 3
 LEVEL-IV - KEY
1) 1 2) 2 3) 2 4) 4 5) 1 6) 1 7) 1 8) 1

LEVEL-IV - HINTS

1. + CCl2 + 4NaOH

(Final product)
2. o- and p-nitrophenols differ in boiling points.
o-nitrophenol is steam volatile
3 . During sulphanation of phenol at law
temparature ortho isomer is major products
where as at 1000 C , it gives mainly para isomer..
4. Both Benzoic acid, phenol react with NaOH.
5. Conceptual.
6. P-nitro phenol is more acidic than o-nitro
phenol.
7. –OH group in phenol is ring activating and ortho
para directing
8. Phenoxide ions are stabilised by resonance but
alkoxide ions are not stabilised by resonance
LEVEL-IV