Alcohols, Phenols and Ethers 327

19 Alcohols, Phenols and Ethers

QUICK LOOK
Hydroboration of Alkene
1
Alcohols: Alcohols are compounds of the general formula 3CH3 − CH = CH2 + B2H6 
→(CH3 − CH2 − CH2 )3 B  3H2O2
OH− / H2O
→
Propene 2 Tripropyl boron
Diborane
ROH, where R is alkyl or substituted alkyl group. The group 3CH − CH − CH − OH + H BO 3CH − CH − CH − OH + H BO
3 2 2 3 3
may be open chain or cyclic, it may contains double bond, a 1− propanol

halogen atom, an aromatic ring or additional hydroxyl groups, Note: In this reaction addition of water to an alkene is syn, anti-
e.g. CH 3CH 2 CH 2 CH 2 OH Markownikoff and free from rearrangement.
Butanol-1

Hydrolysis of ethers: C2 H5 − O − C2 H5 + H 2 O  dil.H 2 SO 4
∆
→
CH2–OH OH
2C 2 H5 OH

By reaction of Grignard reagent with formaldehyde/ other
aldehydes/ ketones
Cyclohexanol
(a) When Grignard reagent reacts with HCHO, it forms
Benzyl alcohol
primary alcohol.
CH2–OH CH=CHCH2OH R
|
H − C = O + RMgX  → H − C − OMgX
| |
H H
(1-cyclo hexene) methanol Cinnamyl alcohol
R
| X
Alcohols can be classified as,  → H − C − OH + Mg
ALCOHOLS | OH
H
(b) Oxirane on reaction with Grignard reagent also forms
Trihydric alcohols primary alcohol.
Monohydric Dihydric alcohols
contains (3-OH groups) O + RMgX  → RCH 2 CH 2 OMgX
alcohols contains (2-OH groups)
Contain (1-OH  CH 2 OH 
 CH2OH    X
roup)    |  
→ RCH 2 CH 2 OH + Mg
e.g.Glycol  |  e.g. Glycerol CHOH 
 OH
 CH OH    (c) Any aldehyde except formaldehyde when treated with
 2   | 
 CH OH  Grignard reagent forms secondary alcohol.
 2 
R
Tertiary |
Primary Secondary R ′ − C = O + RMgX  → R ′ − C − OMgX
R  | |
(RCH 2OH) R    H H
 CHOH   R C OH 
R  R  R
 
| X
Monohydric Alcohols: Preparation  → R ′ − C − OH + Mg
| OH

By oxymercuration - demercuration reaction of alkene: H
CH 3 − CH = CH 2 + (CH 3COO) 2 Hg + H 2 O 
THF
CH 3COOH
→ (d) When 2-alkyl oxirane reacts with Grignard reagent,
 CH 3 − CH − CH 2  secondary alcohol is formed. The ring is opened from least
  NaBH4 / OH− → hindered site.
 | |  
−1/ 2B2 H6 CH 3
 OH HgOCOCH 3  1 |
O + RMgX  → RCH 2 CH 2 OMgX
CH 3 − CH − CH3 + Hg + CH3 COO −
| 3 2
OH CH3
2 − propanol
| X

→ RCH 2 − C − OH + Mg
Note: It is fast and convenient. The addition of water to an | OH
alkene is anti-Markownikoff and free from rearrangement. H
 (e) When ketone reacts with Grignard reagent, it forms
Industrial method for methanol and ethanol are as follows:
tertiary alcohol. CH 4 + H 2 O  Heat
→ CO + 3H 2 ; CO + 2H 2
R R ZnO + CrO3
R′ R′ | R′ | X 
400° C,200atm
→ CH 3 OH
C == O + RMgX  → C — OMgX  → C — OH + Mg we take ethylene obtained from petroleum :
for ethanol
R ′′ R ′′ R ′′ OH
R R CH 2 = CH 2 + H 2O(steam)  H3PO4
300−350° C
→ CH3CH 2OH
R′ | R′ | X It is an Oxo process.
O + RMgX → C — OMgX  → C — OH + Mg
R ′′ R ′′ OH
Primary, Secondary and Tertiary alcohols can be distinguished
by Victor Meyer’s Method:
(f) When 2, 2-dialkyl oxirane reacts with Grignard reagent,
it forms tertiary alcohol. (a) RCH 2 OH  HI
→ RCH 2 I →
AgNO 2
RCH 2 NO 2  OHNO
→
Primary alcohol

R1 R1
R — C — NO 2  NaOH
→ R — C — NO 2
O R1 | | || X ||
+ RMgX 
→ RCH 2 — C — OMgX  → RCH 2 — C — OHNOH + Mg NONa
Nitrolic acid Red sodium salt or nitrolic acid
R2 | | OH
R2 R2 R R R
R1 R1 (b) CHOH → HI
CHI → AgNO 2
CH − NO2
R R R
| | X
MgX 
→ RCH 2 — C — OMgX  → RCH 2 — C — OH + Mg R

OHNO
→ R C − NO2  NaOH
→ Blue colour
| | OH |
R2 R2 NO
Pseudonitolic acid

By reduction of carbonyl compounds R R

(c) R −–C − OH → R −– C − I  → No reaction
HI HNO2

OH R R
C == + 2H 
→ C
H Dihydric Alcohol /Glycol (Ethane – 1, 2- Di-Ol)
The reduction can be carried out by using H 2 /catalyst like Ni, Preparation
Pt, Pd, LiAlH 4 , NaBH 4 , NaH, LiH. When the reduction is 3CH 2 = CH 2 + 2KMnO 4 + 4H 2 O 
→

carried out by using metal/solvent combination it is known as CH 2 — OH

3|+ 2MnO 2 + 2KOH
Bouveault blanc recduction. The intermediates are: CH 2 — OH
−
⋅⋅
⋅−⋅ (Glycol)
R — C — OEt; R — CH — OEt; R — CH. In case of
| | | Trihydric Alcohol Glycerol (Propan - 1, 2, 3 - Triol)
O O. O
. Preparation
metal hydride the reaction intermediate is R 2 — C — O Θ By saponification of oils and fats
| CH 2 — OCOR CH 2 — OH
H | |
CH — OCOR + NaOH → CH — OH + 3RCOONa

By hydrolysis of ester : R1COOR2+KOH 
→ R1COOK | | Soap

+ R2OH CH 2 — OCOR CH 2 — OH
(Glycerol)

By reaction of alkyl boride with CO
O Phenols: Phenols are the organic compounds in which –OH
|| OH group is directly linked to aromatic ring system. The simplest
R 3 B + CO 
→ R 2 — B — C — R 
LiBH 4
→ R 2 BCH → RCH
formula of2 OH
such compound is phenol (C 6 H 5OH). Structure of
|| OH Θ some common phenols is as follows:

→ R 2 — B — C — R → R 2 BCH 
OH
→ RCH 2 OH
H2O OH OH OH OH
R
CH 3

By reaction of primary amines with nitrous acid CH 3
RNH 2 + HNO 2 
→ ROH + N 2 + H 2 O
Phenol o-Cresol m-Cresol CH3

From glucose: C 6 H12 O 6  → 2CH 3 CH 2 OH + 2CO 2
Zymase
p-Cresol
 OH OH Phthalein Reaction
OH OH OH OH
OH
OH OH
+
Catechol Resorcinol OH
Quinol O
||
Preparation: (1) Phenols can be prepared by reaction of C C
O 
conc. H2SO4

or ZnCl2 or AlCl3
→ O
benzene sulphonic acid with NaOH. C C
|| ||
SO 3 H SO 3 Na O O
Phenolphthalei
Phthalic anhydrolic
n
+ NaOH 
→ note that H para to OH is removed.
OH

Ledrer-manasse Reaction: When phenol reacts with formaldehyde

+ H2O 
(i) NaOH
(ii) HCl
→ + Na 2SO 3
in the presence of acid or alkali, it forms bakelite, a thermostat
polymer.
(2) Phenols can also be obtained by warming diazonium salt
OH OH
solution with hot dilute acid solution. OH OH

N2X OH

HCHO
→
H+ or OHΘ

− H2O
→
H+
→ + HX + N2
CH 2 OH
CH 2 CH 2
(3) Phenols can be prepared from aryl halides,
CH 2
Cl OH Bakelite ←  +

300°C
+ NaOH 
200 atm
→ + NaCl OH

(4) By reaction of phenolic acid with soda lime. Liebermann’s Nitroso Reaction

OH
Phenol 
NaNO2 / conc. H 2SO4
→ deep green or blue colour 
H2O
→
OH
+ NaOH(CaO) 
→ + Na 2CO3 Red NaOH
→ green or blue colour. The reactions are as
COOH
follows:
OH OH OH
Kolbe Reaction or Kolbe-schmidt Reaction: When sodium
phenoxide reacts with CO2 at 120°C under 5-7 atmosphere
⊕

NaNO2 / H2SO4
→


↽
⇀


followed by acidification with H, it forms salicylic acid.
ON OH NO NOH
120° C p-nitrosophenol quinone monoxime
+ CO2 →
5−7 atm COON
; H 2SO 4
OH O
⊕
COOH OH

H
→ O
⊕

Saliylic acid
OH
N
← 
NaOH
 ← 
H2O

The reaction intermediate (s) are:
HSO Θ4
⊝ ⊝ N OH
O O OH
⊝ ⊝ N OH
COO COO Phenol indophenol
; ; ON
Sodium salt (Blue)
Phenol indophenol hydrogen
sulphate (Blue)
Nitrosation: If one group has no simple name, the compound may be named
OH OH as an alkoxy derivative:

+ HNO 2 →
H ⊕
CH 3CH 2 CH 2 CHCH 2 CH 3 C2 H5O COOH
o
10 C |
OCH 3
3− Methoxyhexane p − Ethoxybenzoic acid
NO
p-nitrosophenol CH 2 CH 2
| |
Hydrogenation: HO OCH 2 CH 3
OH OH 2 − Ethoxyethanol

The simplest aryl alkyl ether has the special name of anisole.
+ 3H 2  Ni
150− 200° C
→
OCH3

Cyclohexanol
Anisole
Oxidation
If the two groups are identical, the ether is said to be
Phenols turn pink or red or brown when exposed to air and light
symmetrical (e.g., diethyl ether, diphenyl ether), if different,
due to slow oxidation. The exact nature of these oxidation
unsymmetrical (e.g., methyl tert-butyl ether, anisole).
products is not known; but probable products are quinones and
phenoquinones. Preparation of Ethers
In the laboratory, the Williamson synthesis of ethers can be
OH O OH ⋯⋯ HOC 6 H 5 used to make unsymmetrical ethers as well as symmetrical
ethers. In the Williamson synthesis an alkyl halide (or
+ O 2  −  →  2 
C 6 H 5 OH
→
H 2O substituted alkyl halide) is allowed to react with a sodium
alkoxide.
O O⋯⋯ HOC6 H5
quinone Phenoquinone → R − O − R ′ + Na + X −
R − X + Na + − O − R ′ 
When phenols is oxidised with potassium persulphate in Example
alkaline solution, it forms quinol and the reaction is known as CH3 CH 3
Elbs persulphate oxidation. | |
+ −
CH3Br + Na O — C — CH3 
→ CH 3 — O — C — CH 3
OH OH | |
CH3 CH 3
Sodium tert-butoxide tert -Butyl methyl ether
 K →
2S2 O 8
OH Θ
Reaction involves nucleophilic substitution of alkoxide ion for
O halide ion; it is strictly analogous to the formation of alcohols
quinol
by treatment of alkyl halides with aqueous hydroxide.
Structure and Nomenclature of Ethers
Ethers are compounds of the general formula R ′O − + → R ′O — R
R — X  + X−
Nucleophile Substrate Leaving group
R–O–R, Ar–O–R, or Ar – O –Ar.
Since alkoxides and alkyl halides are both prepared from
To commonly name ethers we usually name the two groups that
alcohols, the Williamson method ultimately involves the
are attached to oxygen, and follow these names by the word
synthesis of ether from two alcohols.
ether:
If we wish to make unsymmetrical dialkyl ether, we have a
choice of two combinations of reagents; one of these is nearly
C 2 H 5 OC 2 H 5 −O − always better than the other. In the preparation of tert-butyl ethyl
Ethyl ether Phenyl ether ether, for example, the following combinations are conceivable:
CH3 CH3 CH3
| | |
CH3 — O — C — CH3 CH3 — C — O — CH3CH 2 — O — C — CH3
| | |
CH3 H CH3
Methyl tert -butyl ether Isopropyl phenyl ether tert -Butyl ethyl ether
 CH3 Chemical Properties
| HCl ɺɺ – C H ]+ Cl −
CH3CH 2 Br + Na + −O — C — CH3 Feasible [C 2 H 5 – OH 2 5
Diethyl oxonium chloride
|
CH3 H2SO4 ɺɺ – C H ]+ HSO −
[C 2 H 5 – OH 2 5 4
Diethyl oxonium hydrogen sulphate

CH3 C2 H5
| BF3 ɺɺ : 
O → BF3
CH3 — C — Cl + Na + −OCH 2CH3 Not Feasible Boron triflouride etherate
| C2 H5
CH3 CH3
C2 H5 | C2H5
CH3MgBr
Which do we choose? Alkoxides are not only nucleophiles, but ɺɺ
O: 
→Mg ← :O
ɺɺ
also strong bases which tend to react with alkyl halides by C2 H5 | C2H5
Br
elimination, to yield alkenes. Whenever we are trying to carry
HI, 373 K
out nucleophilic substitution, one must be aware of the danger C 2 H 5OH + C 2 H 5 I
Limited amount
Ethyl alcohol Ethyliodide
of a competing elimination reaction. The tendency of alkyl HI in excess
2C 2 H 5 I + H 2 O
halides to undergo elimination is 3° > 2° > 1°. 373 K

2H5OC2H5 Conc. H2SO4

C 2 H 5Cl + C 2 H 5 HSO 4
Diethylether ∆
In the above example, the use of the tertiary halide is rejected PCl5
2C 2 H 5Cl + POCl3
as it would be expected to yield mostly or all elimination
2C2H5Cl + POCl3
product; hence the other combination is used. Ethers are the anhyd ZnCl2
C 2 H 5Cl + CH 3COOC 2 H 5
Ethyl acetate
alkoxy derivatives of alkanes with general formula R OR ′. If R
CH3CO-O-COCH3
2CH 3COOC 2 H 5
and R′ are same they are simple ethers while If R and R′ are anhyd AlCl3
O — OH
different they are mixed ethers. |
O2 Oxidation
CH 3 — CH — O — CH 2 — CH 3
Preparation of Ethers air and light
Diethyl ether hydroperox ide

Willlamson’s synthesis Cl2 Halogenation

dark
CH 3 — CH — O — CH 2 H 5 
Cl2
dark
→
C2 H 5ONa + C 2 H 5 Br 
→ |
Sod. ethoxide Ethyl bromide Cl
α-chlorodiethyl ether
Dehydration of alcohol CH 3 — CH — O — CH — CH 3
| |
C2 H 5OH + C2 H 5OH →
conc. H 2SO4
413 K Cl Cl
C2H5OC2H5
Diethyl ether

α , α ′− dichlorodiethyl ether

From diazomethane Cl2 Halogenation

CCl3 − CCl2 − O − CCl2 − CCl3 +10 HCl
Sunlight
C2 H5 OH + CH 2 N 2  →
HBF4 Perchlorodiethyl ether

Diazomethane

Reaction of alkyl halide Reactions of Aromatic Ethers

with dry silver oxide OCH 3 OCH 3
(CH3CH 2 Br)2 + Ag 2O 
→ ∆ Br Br
+

o-bromo anisole
Reactions of Ethers Cleavage by Acids Br
OCH 3 OH o-bromo anisole
Ethers are comparatively unreactive compounds. The ether
linkage is quite stable toward bases, oxidizing agents, and
CH3 I
reducing agents. In so far as the ether linkage itself is concerned,
ethers undergo just one kind of reaction, cleavage by acids: Methoxy benzene
OCH 3 OCH 3
or Anisole
→ R − X + R′ − OH → R ′ − X
R − O − R ′ HX  HX
NO2
+
Reactivity of HX: HI > HBr > HCl
o-nitro anisole
Cleavage takes place only under quite vigorous conditions: NO2
concentrated acids (usually HI or HBr) and high temperatures. o-nitro anisole
MULTIPLE CHOICE QUESTIONS 12. An organic compound X on treatment with acidified
Structure and Nomenclature of Ethers K 2 Cr2 O 7 gives a compound Y which reacts with I2 and

1. The reaction of ethylene glycol with PI3 gives: sodium carbonate to form tri-odomethane. The compound
X is?
a. ICH 2 CH 2 I b. CH 2 == CH 2
a. CH 3 OH b. CH 3 − CO − CH 3
c. CH 2 == CHI d. ICH == CHI
c. CH 3 CHO d. CH 3 CH(OH)CH 3
2. The compound ‘A’ when treated with ceric ammonium
nitrate solution gives yellow ppt. The compound ‘A’ is? 13. The reaction of conc. HNO3 and phenol forms:
a. Alcohol b. Aldehyde c. Acid d. Alkane a. Benzoic acid b. Salicylic acid
c. o-and p-nitrophenol d. Picric acid
3. Which of the following product is formed, when ether is
exposed to air? 14. Phenol is:
a. Oxide b. Alkanes a. A weaker base than NH 3
c. Alkenes d. Peroxide of diethyl ether b. Stronger than carbonic acid
4. During dehydration of alcohols to alkenes by heating with c. Weaker than carbonic acid
conc. H2SO4 the initiation step is: d. A neutral compound
a. Protonation of alcohol molecule 15. Phenol at 25ºC is:
b. Formation of carbocation a. A white crystalline solid
c. Elimination of water b. A transparent liquid
d. Formation of an ester c. A gas
5. Phenol is less acidic than: d. Yellow solution
a. Ethanol b. Methanol 16. At low temperature phenol reacts with Br2 in CS2 to form:
c. o-nitrophenol d. p-methylphenol
a. m-bromophenol b. o-and p-bromophenol
6. Primary alcohols on dehydration give: c. p-bromophenol d. 2, 4, 6-tribromophenol
a. Alkenes b. Alkanes
17. Oxidation of ethanol by chromic acid forms:
c. Both a. and b. d. None of these
a. Ethanol b. Methanol
7. Primary and secondary alcohols on action of reduced copper c. 2-propanone d. Ethanoic acid
give:
a. Aldehydes and ketones respectively 18. Methanol and ethanol are miscible in water due to:
b. Ketones and aldehydes respectively a. Covalent character
c. Only aldehydes b. Hydrogen bonding character
d. Only ketones c. Oxygen bonding character
d. None of these
8. Methyl alcohol on oxidation with acidified K 2 Cr2 O 7 gives:
19. By distilling glycol with fuming sulphuric acid, which of
a. CH 3 COCH 3 b. CH 3 CHO
following is obtained?
c. HCOOH d. CH3 COOH a. Glycerol b. Pinacol
9. Ethyl alcohol on oxidation with K 2 Cr2 O7 gives: c. Dioxan d. Ethylene oxide

a. Acetic acid
c. Formaldehyde
10. Lucas test is used for:
a. Alcohols
c. Diethyl ether
11. When phenol reacts with ammonia in presence of ZnCl 2 at
300°C, it gives?
a. Primary amine
c. Tertiary amine
b. Acetaldehyde
d. Formic acid
b. Amines
d. Glacial acetic acid
b. Secondary amine
d. Both (b) and (c)
20. The compound which gives the most stable carbonium ion
on dehydration is?
CH 3
|
a. CH 3 — CH — CH 2 OH b. CH 3 — C — OH
| |
CH 3 CH 3
c. CH 3 — CH 2 — CH 2 — CH 2 OH
CH 3
|
d. CH 3 — CH — CH 2 — CH 3
General Introduction of Alcohol, Phenol and Ethers 31. Acetone on treatment with CH 3 − Mg − I and on further
21. Butanal is an example of: hydrolysis gives:
a. Primary alcohol b. Secondary alcohol a. Isopropyl alcohol b. Primary alcohol
c. Aliphatic aldehyde d. Aliphatic ketone c. Acetic acid d. 2-methyl 2-propanol
22. Methylated spirit is: 32. Which gas is eliminated in fermentation?
a. Methanol b. Methanol + ethanol a. O2 b. CO 2
c. Methanoic acid d. Methanamide
c. N 2 d. H 2
23. Which of the following is dihydric alcohol?
a. Glycerol b. Ethylene glycol 33. Commercially methanol is prepared by:
c. Catechol d. Resorcinol a. Reduction of CO in presence of ZnO.Cr2 O 3
24. According to Lewis concept of acids and bases, ether is: b. Methane reacts with water vapours at 900°C in
a. Acidic b. Basic presence of Ni catalyst
c. Neutral d. Amphoteric c. Reduction of HCHO by LiAlH 4
d. Reduction of HCHO by aqueous NaOH
Preparation of Alcohol, Phenol and Ethers
25. Ethanol is prepared industrially by: 34. From Williamson’s synthesis preparation of which of
a. Hydration of ethylene b. Fermentation of sugars following is possible?
c. Both the above d. None of these a. Only symmetrical ethers b. Only symmetrical ethers
c. Both types d. None of these
26. Ethyl alcohol is industrially prepared from ethylene by:
a. Permanganate oxidation 35. In the reaction Ar − OH + Rx 
alkali
→ A, A is:
b. Catalytic reduction a. An aldehyde b. An aryl chloride
c. Absorbing in H 2SO4 followed by hydrolysis c. An ether d. A ketone
d. Fermentation 36. The compound formed when ethyl bromide is heated with
27. Propene, CH3 − CH = CH 2 can be converted to 1-propanol dry silver oxide is:
a. Dimethyl ether b. Diethyl ether
by oxidation. Which set of reagents among the following
c. Methyl alcohol d. Ethyl alcohol
is ideal to effect the conversion?
a. Alkaline KMnO4 37. The reagent used for the preparation of higher ether from
halogenated ethers is:
b. B2 H6 and alkaline H2 O2
a. conc. H 2 SO 4 b. Sodium alkoxide
c. O3 / Zn dust
c. Dry silver oxide d. Grignard reagent
d. OsO4 / CH 4 ,Cl2
38. Acetyl bromide reacts with excess of CH 3 MgI followed
28. Coconut oil upon alkaline hydrolysis gives:
by treatment with a saturated solution of NH 4 Cl gives:
a. Glycol b. Alcohol
a. 2-methyl-2-propanol b. Acetamide
c. Glycerol d. Ethylene oxide
c. Acetone d. Acetyl iodide
29. In the commercial manufacture of ethyl alcohol from
starchy substances by fermentation method, which 39. What is obtained when chlorine is passed in boiling toluene
enzymes stepwise complete the fermentation reaction? and product is hydrolysed?
a. Diastase, maltase and zymase a. o-Cresol b. p-Cresol
b. Maltase, zymase and invertase c. 2, 4-Dihydroxytoluene d. Benzyl alcohol
c. Diastase, zymase and lactase 40. In which case methyl-t-butyl ether is formed?
d. Diastase, invertase and zymase a. (C2 H 5 )3 CONa + CH 3 Cl
30. If formaldehyde and potassium hydroxide are heated, then b. (CH 3 )3 CONa + CH 3 Cl
we get:
c. (CH 3 )3 CONa + C 2 H 5 Cl
a. Acetylene b. Methane
c. Methyl alcohol d. Ethyl formate d. (CH 3 )3 CONa + CH 3 Cl
41. C6 H5 − CH = CHCHO 
X
→ C6 H5 CH = CHCH 2 OH. In 50. Read the following statements carefully:
the above sequence X can be: a. A secondary alcohol on oxidation gives a ketone
a. H 2 / Ni b. NaBH 4 b. Ethanol reacts with conc. H 2 SO 4 at 180°C to yield ethylene
c. Methanol reacts with iodine and sodium hydroxide to
c. K 2 Cr2 O7 / H + d. Both a.and b.
give a yellow precipitate of iodoform
42. Methylphenyl ether can be obtained by reacting: d. Hydrogen gas is liberated when sodium is added to
a. Phenolate ions and methyl iodide alcohol. Select the correct statements from the above set:
b. Methoxide ions and bromobenzene a. A, B b. C, D c. A, B, D d. A, C, D
c. Methanol and phenol
51. The reagent used for the dehydration of an alcohol is:
d. Bromo benzene and methyl bromide
a. Phosphorus pentachloride
Properties of alcohol, Phenol and Ethers b. Calcium chloride
43. Methyl alcohol can be distinguished from ethyl alcohol c. Aluminium oxide
using: d. Sodium chloride
a. Fehling solution 52. When rectified spirit and benzene are distilled together,
b. Schiff's reagent the first fraction obtained is?
c. Sodium hydroxide and iodine a. A ternary azeotrope b. Absolute alcohol
d. Phthalein fusion test c. A binary azeotrope d. Denatured spirit
44. For phenol, which of the following statements is correct? 53. Which of the following is most acidic?
a. It is insoluble in water? a. Phenol b. Benzyl alcohol
b. It has lower melting point compared to aromatic c. m-chlorophenol d. Cyclohexanol
hydrocarbons of comparable molecular weight
54. Which is not correct?
c. It has higher boiling point than toluene
a. Phenol is more acidic than acetic acid
d. It does not show acidic property
b. Ethanol is less acidic than phenol
45. Final product formed on reduction of glycerol by hydroiodic c. Ethanol has lower boiling point than ethane
acid is: d. Ethyne is a non-linear molecule
a. Propane b. Propanoic acid
c. Propene d. Propyne Uses of alcohol, Phenol and Ethers
55. Glycerol is used in the manufacture of:
46. Which of the following explains the viscous nature of
a. Dynamite b. Varnish
glycerol?
c. Paints d. Soft drinks
a. Covalent bonds b. Hydrogen bonds
c. Vander Wall's forces d. Ionic forces 56. Alcoholic fermentation is brought about by the action of:
47. The alcohol that produces turbidity immediately with a. CO 2 b. O2 c. Invertase d. Yeast
ZnCl 2 + conc. HCl at room temperature: 57. In order to make alcohol undrinkable pyridine and
a. 1-hydroxybutane methanol are added to it. The resulting alcohol is called:
b. 2-hydroxybutane a. Power alcohol b. Proof spirit
c. 2-hydroxy-2-methylpropane c. Denatured spirit d. Poison alcohol
d. 1-hydroxy-2-methylpropane 58. Main constituent of dynamite is:
48. The alcohol which easily reacts with conc. HCl is? a. Nitrobenzene b. Nitroglycerine
a. CH 3 − CHOH − CH 2 − CH 3 c. Picric acid d. TNT
b. (CH 3 )3 − C − OH 59. The Bouveault-Blanc reduction involves:
c. CH 3 − CH 2 − CH 2 − CH 2 − OH a. C 2 H 5 OH / Na b. LiAlH 4
d. (CH 3 )3 − CH − CH 2 OH c. C2 H 5 MgX − d. Zn / HCl
49. A compound that easily undergoes bromination is: 60. Which is used as antifreeze?
a. Phenol b. Toluene a. Glycol b. Ethyl alcohol
c. Benzene d. Benzoic acid c. Water d. Methanol
NCERT EXEMPLAR PROBLEMS 67. Phenol has higher pka value than:
More than One Answer a. acetic acid
b. p-methoxy phenol
61. Alkenes convert into alcohols by:
c. p-nitrophenol
a. Hydrolysis by dil. H2SO4
b. Hydration of alkene by alkaline KMnO4 d. ethanol
c. Hydrolysis by water vapours and conc. H2SO4 68. Which of the following reactions can be used to prepare
d. Hydration of alkene by aqueous KOH methyl phenyl ether?
62. The following ether, when treated with HI produces: a. reacting sodium phenoxide with methyl chloride
b. reacting phenol with diazomethane (CH 2 N 2 )
—O — CH 2 — + HI 
→
c. reacting sodium methoxide with chlorobenzene
d. reacting C6 H 5 OMgCl with chloromethane
—CH 2 —CH 2 OH
a. b.
69. Carbinol is:
a. C2 H5 OH b. CH3OH
c. —I d. — OH
c. (CH3 )2 CHOH d. CH3 CH 2 CH(OH)CH3

63. Structure of compound X is: 70. Wood spirit is known as:

OH O a. Methanol b. Ethanol
c. Acetone d. Benzene

Assertion and Reason

Note: Read the Assertion (A) and Reason (R) carefully to mark
OH OH OH
the correct option out of the options given below:
Than which of the following statements are correct?
a. If both assertion and reason are true and the reason is the
a. X have two stereoisomers
correct explanation of the assertion.
b. All stereomers of X have the same melting point
b. If both assertion and reason are true but reason is not the
c. X reaction with SOCl 2 followed by alcoholic KOH
correct explanation of the assertion.
product E which containing 8π bonds c. If assertion is true but reason is false.
d. None of these d. If the assertion and reason both are false.
64. An organic compound X of molecular formula C4 H10 O e. If assertion is false but reason is true.
undergoes oxidation to give a compound Y of molecular 71. Assertion: Phenol is more reactive than benzene towards
formula C4 H8O 2 . X could be: electrophilic substitution reaction.
a. CH3CH 2CH 2 CH 2 OH b. CH 3CH 2 CH(OH)CH3 Reason: In the case of phenol, the intermediate carbocation
is more resonance stabilized.
c. (CH 3 ) 2 CHCH 2 OH d. (CH 3 )3 COH
72. Assertion: Phenol undergo Kolbe reaction, ethanol does
65. Which of the following methods is/are not the industrial
not.
methods to prepare methanol?
Reason: Phenoxide ion is more basic than ethoxide ion.
a. catalytic reduction of carbon monoxide in presence of
ZnO − Cr2 O 3 73. Assertion: Lucas reagent is a mixture of anhydrous ZnCl 2
b. reacting methane with steam at 900°C with a Ni catalyst and concentrate HCl.
c. reducing formaldehyde with lithium aluminium hydride Reason: Primary alcohol produce ppt. with Lucas reagents.
d. reacting formaldehyde with aqueous sodium hydroxide
74. Assertion: Resorcinol turns FeCl 2 solution purple.
solution
Reason: Resorcinol have phenolic group.
66. Which of the following reagent (s) or test (s), can be used
to distinguish 2 methyl propanol and 2-methyl propanol – 2? 75. Assertion: The major products formed by heating
a. I2 / NaOH b. HCl/anhyd. ZnCl 2 C6 H 5 CH 2 OCH 3 with HI are C6 H 5CH, I and CH 3OH.
c. Victor-Meyer test d. oxidation with Cu at 573 K Reason: Benzyl cation is more stable than methyl cation.
76. Assertion: The pka of acetic acid is lower than that of phenol. (a) Both reactions are protonated by acids.
Reason: Phenoxide ion is more resonance stabilized. (b) The reactivity of alcohols decrease in the order, tertiary >
77. Assertion: Alcoholic fermentation involves conversion of secondary>primary due to the formation of stable carbocations,
sugar into ethyl alcohol by yeast. which is stabilized by hyperconjugation and +I effect. The
Reason: Fermentation involves the slow decomposition of dehydration of alcohol follows three steps mechanism for acid-
complex organic. base catalysed dehydration of least stable tertiary butyl alcohol,
78. Assertion: Acid catalysed dehydration of t-butanol is i.e., (CH 3 )3 COH 
H 2SO4
∆
→ (CH 3 ) 2 C = CH 2 + H 2 O
slower than n-butanol. In step I, protonation (acid catalysed) of tert-butyl alcohol takes
Reason: Dehydration involves formation of the protonated place. In step II, dissociation of tert-butyloxenium ion takes
alcohol, ROH +2 . place followed by formation of carbocation. Alkene is formed
79. Assertion: Tertiary alcohols give turbidity immediately in step III by deprotonation (base catalysed) of tert-butyl cation.
with Lucas reagent. H
CH 3
Reason: A mixture of conc. HI + anhydrous ZnCl 2 is called
Step (i): H3C ɺɺ
O + O: 
Fast
− H2 O
→
Lucas reagent. ɺɺ H
CH3
H H
80. Assertion: The ease of dehydration of alcohols follows
the order. Primary > Secondary > Tertiary. CH3 + H
Reason: Dehydration proceeds through the formation of H3 C O
CH3 H
oxonium ions.
81. Assertion: Phenol reacts with acyl halides in presence of CH3 + H CH 3
pyridine to form phenyl acetate. Step (ii): H3C O 
Slow
− H2 O
→ H3C — +
CH3 H CH 3
Reason: Benzoylation of phenol is carried out in the
presence of NH 4 OH. H3C H3C
+ −H +
Step (iii):  → CH2
82. Assertion: Treatment of phenol with nitrous acid yields p- H3C H H3C
benzoquinone monoxime. Another important reaction of alcohols is iodoform reaction
Reason: p-nitrosophenol and p-benzoquinone monoxime given by ethanol (in primary alcohols) and are secondary
are tautomers.
alcohols having 2-ol nature. Such alcohols give yellow ppt. of
83. Assertion: Reimer-Tiemann reaction of phenol with CCl 4 in CHI3 with NaOH and I2 solution.
NaOH at 340 K gives salicylic acis as the major product.
86. Why dehydration of vinyl alcohol is not difficult?
Reason: The reaction occurs through intermediate formation
a. Due to high enthalpy of vinylic —C — OH bond
of dichlorocarbene.
b. Due to unstable nature of == C — OH bond by tautomerism
84. Assertion: Both symmetrical and unsymmetrical ethers
can be prepared by Williamson’s synthesis. c. Carbocation never forms in case of vinyl alcohol
Reason: Williamson’s synthesis is an example of d. Both (a) and (b) are correct
nucleophilic substitution reaction. 87. Which carbocation will not form an intermediate?
85. Assertion: (CH 3 )3 − Br and CH 3CH 2 ONa react to form +
a. (C 6 H 5 ) 3 C b. ⊕
(CH 3 )3 C − O − CH 2 CH 3 .
Reason: Good yields of ethers are obtained when tert- ⊕
alkyl halides are treated with alkoxides. +
c. d. CH 3 == C H

Comprehension Based
Paragraph –I 88. Which will give iodoform test?
The dehydration of alcohols and the conversion of alcohols to a. 2-methylpropan-2-ol
alkyl halides by treatment of hydrogen halides are similar in b. Ethyl acetoacetate
two important ways suggesting the formation of carbocation as c. 2-methylbutan-2-ol
key intermediate. d. 3-methylpentant-2-ol
89. Iodoform reaction is given by molecules having CH3 —C — (D) PhCH 2 CHO + CH 3 M gI 4. CH 3CH 2 CH 2 OH
||
O (E) CH 3CHO + PhMgBr 5. PhCH2CH(OH)CH3
unit or CH 3 — CHOH unit attached to carbon or H-atom. a.A→1; B→2; C→3; D→4; E→5
| b. A→1; B→2; C→4; D→5; E→3
COR c. A→3; B→2; C→5; D→4; E→1
However H 2 C and CH 3 ⋅ CO ⋅ CH 2 COOC 2 H 5
COR d. A→5; B→1; C→4; D→3; E→2
does not give iodoform reaction because: 94. Match the column.
a. I2 reacts at active H-atom Column I Column II
b. I2 reacts at α -methyl group (A) Wood spirit 1. Trinitroglycerine and
c. I2 does not react with these molecule dinitroglycerine
d. Hydrolysis of iodide substituted molecule does not (B) Fermentation 2. Methyl alcohol
occur (C) Glycerine 3. ethyl alcohol
(D) Lucas test 4. Propane-1, 2, 3-triol
90. The reagent used to distinguish 1-cycloethanol and 2-cycl-
(E) Dynamite 5. Tertiary alcohol
oethanol is:
a.A→1; B→2; C→3; D→5; E→4
a. soda lime b. NaOH + H 2 O
b. A→4; B→3; C→2; D→1; E→5
c. acidified KMnO 4 d. (aq.) FeCl3
c. A→3; B→2; C→1; D→4; E→5
91. An alcohol on iodoform reaction give iodoform and d. A→2; B→3; C→4; D→5; E→1
sodium salt of unsaturated acid containing 3 carbon atoms. 95. Match the column.
The alcohol is:
Column I Column II
a. but-3-en-2-ol b. prop-2-en-2-ol
(A) Etherates 1. Estimation of methoxy or
c. pent-3-en-2-ol d. 3-methyl-but-3-en-2-ol
ethoxy groups
Match the Column (B) Williamson’s 2. Ether + BF3
92. Match the column. synthesis
Column I Column II (C) Zeisel method 3. Ether + mineral acid
(A) Absolute alcohol 1. Isopropyl alcohol (D) Oxonium salts 4. RX + R ′ONa
(B) Denaturated spirit 2. Anhydrous alcohol (E) Phenetol 5. C6 H 5OH + (C2 H 5 ) 2 SO 4 pres
(C) 80º proof alcoholic 3. 20% absolute alcohol + ence of NaOH
liquor 80% gasoline a.A→1; B→2; C→3; D→4; E→5
(D) Power alcohol 4. alcoholic liquors cont- b. A→4; B→3; C→5; D→1; E→2
aining 40% ethanol c. A→2; B→4; C→1; D→3; E→5
(E) Power alcohol 5. Ethanol containing d. A→2; B→1; C→4; D→3; E→5
CH 3OH and pyridine.
Integer
a.A→1; B→2; C→3; D→4; E→5
b. A→2; B→5; C→4; D→1; E→3 96. The vapour density of C2 H5OH is?
c. A→3; B→2; C→1; D→5; E→4 97. 10 gm of a mixture of hexane and ethanol reacts with
d. A→2; B→1; C→4; D→3; E→5 sodium to give 200 ml. of H2 at 27°C and 760 mm pressure.
93. Match the column. The percentage of ethanol is?
Column I Column II
98. Number of metamers represented by molecular formula
(A) CH 3CH 2CH 2 MgBr + H 2 O 1. CH3 (CH2 )2 CH2OH
C 4 H10 O is:
(B) CH 3 CH 2 CH 2 COCH 3 2. (CH3 )2 C(OH)CH2
99. What amount of bromine will be required to convert 2 g
+ CH 3 MgI CH 2 CH3
of phenol into 2, 4, 6-tribromophenol?
O 3. CH3CH(Ph)OH
100. One mole of phenol reacts with bromine to form
(C) CH 3 MgI + CH 2 — CH 2
tribromophenol. How much bromine is used?
ANSWER 7. (a) R —CH 2 OH 
Cu
→ R — CHO + H 2
1o alcohol
1. 2. 3. 4. 5. 6. 7. 8. 9. 10.
b a d a c a a c a a R — CH — R 
Cu
→ R — C — R + H2
| ||
11. 12. 13. 14. 15. 16. 17. 18. 19. 20. OH O
2º alcohol
a d d c a b d b c b
21. 22. 23. 24. 25. 26. 27. 28. 29. 30.
8. (c) CH 3 OH 
K 2 Cr2 O 7
→ HCOOH
c b b b c c b c a c H 2 SO 4

31. 32. 33. 34. 35. 36. 37. 38. 39. 40.
d b a c c b d a d b 9. (a) CH 3 CH 2 OH 
K 2 Cr2 O 7
→ CH 3 COOH
41. 42. 43. 44. 45. 46. 47. 48. 49. 50. 10. (a) Lucas test is used for the distinction of primary
b a c c c b c b a c
secondary and tertiary alcohols.
51. 52. 53. 54. 55. 56. 57. 58. 59. 60.
c a c a a d c b a a OH NH2
61. 62. 63. 64. 65. 66. 67. 68. 69. 70.
b,c a,d a,b,c a,c b,c,d b,c,d a,c a,b b a 11. (a) + NH 3 
ZnCl2
300ºC
→ + H2O
71. 72. 73. 74. 75. 76. 77. 78. 79. 80.
a c c a a c a e c e
81. 82. 83. 84. 85. 86. 87. 88. 89. 90.
12. (d) CH 3 — CH — CH3 
K 2 Cr2 O7
H 2SO4
→ CH3 — C — CH 3
| ||
c b c b d d c d a b
OH O
91. 92. 93. 94. 95. 96. 97. 98. 99. 100.
a b b d c 23 10 3 10.22 3 
NaOH
I2
→ CHI3 + CH3 COONa
Yellow ppt

SOLUTION OH OH
Multiple Choice Questions O2N NO2
13. (d) conc. HNO3 
H 2SO 4
→
(conc.)
CH 2 OH CH 2 I
1. (b) | + PI3 
→ | →
− I2
CH 2 == CH 2
CH 2 OH CH 2 I NO2
Picric acid
2. (a) R — OH + (NH 4 ) 2 Ce(NO3 )6 
→
alcohol Cerric amm. nitrate 14. (c) Phenol is weaker acid than carbonic acid
Ce(NO3 ) 6 (ROH)9 + 2N + 14NO3 15. (a) C6 H5 OH H 2 CO 3 CH3 COOH
yellow ppt.
−8 −10 −7
K a = 10 − 10 , K a = 10 K a = 10 −5
3. (d) C2 H5 — O — C2 H5 + O2 
→ hv
25ºC
OH OH OH
CH 3 — CH(OOH) — O — C 2 H 5
Br
4. → H + + HSO 4−
(a) H 2SO 4 
16. (b) + Br2 
CS2
→ +
⊕ o -bromophenol
C 2 H 5 OH + H + 
Protonation
of alcohol
→ C 2 H 5 — O— H Br
↓ p -bromophonol
H In presence of non-polar solvent (CS2 ) the ionization of
Protonated alcohol

phenol is suppressed. The ring is slightly activated and

OH OH
hence mono substitution occurs.
NO2 On the other hand with Br2 water phenol forms 2,4,6-
5. (c)
tribromo phenol.
OH OH
Nitro group is electron with-drawing. Hence, increases
acidic nature. Br Br
+ 3Br2 
water
→ + 3HBr
6. (a) R — CH 2 — CH 2 — OH 
Conc.H 2 SO 4
170o C
→
1o alcohol
Br
R — CH == CH 2 + H 2 O
Alkene In aqueous solution phenol ionizes to give phenoxide ion.
 Due to the presence of negative charge on oxygen the (CH 3 CH 2 CH3 )3 B 
H 2 O2
→ 3CH3 CH 2 CH 2 − OH
benzene ring is highly activated and hence trisubstituted
product is obtained. 28. (c) Coconut oil + Alkali → Soap + Glycerol
It is a saponification reaction.
17. (d) C 2 H 5 OH 
CrO3
→ CH 3 COOH
Ethyl alcohol Acetic acid 29. (a) 2(C6 H10 O5 ) n + nH 2 O →
Diastase
n (C12 H 22 O11 )
Starch (from germinated barley) Maltose
18. (b) Hydrogen bonding:
δ− δ+ δ− δ+ δ− δ+
C12 H 22 O11 + H 2 O → 2 C6 H12 O 6
Maltase
(from yeast)
O— H⋅⋅⋅ O— H⋅⋅⋅ O— H Glucose

| | | C6 H12 O6 → 2C 2 H 5 OH + 2CO 2

Zymase

R H R (from yeast)
Alcohol Water Alcohol

30. (c) HCHO + HCHO 

Conc.KOH
→ CH3 OH + HCOOK
CH 2 CH 2 Methyl alcohol Potassium formate

19. (c) HO OH 

Fuming
→ It is cannizzaro’s reaction.
HO OH H2SO4
CH 2 CH 2 31. (d) Acetone reacts with Grignard’s reagent to give tertiary
Ethylene glycol
alcohol.
CH 2 CH 2
O O + 2H 2 O (CH3 )2 C = O + CH3 MgBr 
H2 O
→ (CH3 )3 C − OH
CH 2 CH 2 ter-butyl alcohol

20. (b) Tertiary carbonium ion is the most stable and it will be 32. (b) C6 H12 O 6 → 2C 2 H 5 OH + 2CO 2
Zymase

Glucose
given by dehydration of tertiary alcohol.
During fermentation CO 2 gas is eliminated.
21. (c) Butanal CH3 − CH2 − CH 2 − CHO, an aliphatic aldehyde.
CuO − ZnO − Cr2 O3
22. (b) 5-10% methyl and remaining ethanol is called 33. (a) CO + H 2  → CH3 OH
573K, 200 atm Methanol
methylated spirit. It is also known as denatured alcohol
because it is unfit for drinking. 34. (c) CH 3 CONa + Br − CH 3 
→ CH 3 − O − CH 3 + NaBr
Dimethyl ether
(symmetrical ether)
23. (b) Glycols are dihydric alcohols (having two hydroxyl
groups). Ethylene glycol is the first member of this series. CH3 CH3
| |
−
CH 2 OH CH 3 − C− O Na + CH 3 Br 
→ CH 3 − C− OCH 3 + NaBr
| | |
CH2OH CH3 CH3
(Ethylene glycol) Methyl ter-butyl ether
(unsymmetrical ether)

24. (b) Ether is basic because lone pairs of electrons are

OH O-R
••
present on oxygen atom, R − O− R.
••
35. (c) + RX 
Alkali
→ + HX
25. (c) Hydration of alkenes
+ − 36. (b) 2C 2 H 5 Br + Ag 2 O 
→ C 2 H 5 − O − C 2 H 5 + 2AgBr
CH 2 = CH 2 + HHSO 4  → CH 3 − CH 2 − HSO 4 Dry

CH3 − CH2HSO4 

→CH3 − CH2 − OH + H2SO4
H2O
If we take moist Ag 2 O then alcohol is formed
Boil

Fermentation of sugars: Ag 2 O + H 2 O 
→ 2AgOH
C12 H22 O11 + H2 O 
→ C6 H12 O6 + C6 H12 O6
Invertase
C2 H5 Br + AgOH 
→ C2 H5 OH + AgBr
Glucose Fructose

C H O 
Zymase
6 12 6 → 2C2 H 5 OH + 2CO 2 37. (d) CH 3 OCH 3 
Cl2 / hv
→ CH 3 OCH 2 Cl
Glucose or Fructose Methoxymethane α− Chlorodimethyl ether
(Lower ether)

26. (c) CH2 = CH2 

H2SO4
→CH3 − CH2 − HSO4 
CH 3 MgBr
→ CH 3 OCH 2 CH 3
− MgBr (Cl) Methoxyethane

→ CH3CH 2 − OH + H2SO4
Hydrolysis
(Higher ether)

27. (b) Hydroboration oxidation (Industrial preparation of O CH3

|| |
alcohol) 38. (a) CH 3 − C − Br  → CH 3 − C− OH
(i) Excess-CH3 MgI

Acetyl bromide (ii) Saturated NH 4 Cl |

1 CH3
3CH3 CH = CH 2 + B2 H 6 →
Dry
(CH 3CH 2 CH3 )3 B
2 ether 2-methyl 2-propanol
39. (d) When chlorine is passed in boiling toluene, substitution 48. (b) Tertiary alcohol readily reacts with halogen acid
inside chain takes place and benzyl chloride is obtained CH 3 CH 3
which on hydrolysis give benzyl alcohol. ↓ |

CH3 CH2Cl CH2OH CH 3 → C − OH → CH 3 − C + + OH −

↑ |

CH 3 CH 3
→
Cl2

H.OH
→
Presence of 3 alkyl group increases electron density on 3°
toluene Benzyl chloride Benzyl alcohol
carbon atom. Hence –OH group is easily removed. After
CH3 the removal of –OH group 3° carbonium ion is formed
| which is most stable
40. (b) CH 3 − C− O − Na + Cl − CH 3 
→
|
CH3 49. (a) A compound that undergoes bromination easily is
2, 2 dimethyl sodium ethoxide phenol. Due to presence of –OH group the ring becomes
CH3 much more active in substitution reactions. The
|
CH 3 − C− O − CH 3 + NaCl bromination occurs due to availability of electrons on
|
ortho and para position.
CH3
Methyl-t butyl ether
50. (c) (a) CH 3 − CH − CH 3 
Oxidation
→ CH 3 − C − CH 3
| ||
41. (b) NaBH 4 and LiAlH 4 attacks only carbonyl group and OH O
reduce it into alcohol group. They do not attack on double Conc. H SO
(b) CH 3 − CH 2 − OH  2
→ CH 2 = CH 2 + H 2 O
4

bond. 180o C

C6 H5 − CH = CHCHO 
NaBH 4
→ (d) 2CH3CH 2 OH + 2Na 
→ 2CH3 − CH 2 − ONa + H 2
cinnamic aldehyde
Al 2 O 3
C2 H5 OC 2 H 5 + H 2 O
C6 H 5 − CH = CH.CH 2 OH
cinnamic alcohol 250o C Diethyl ether
42. (a) C6 H6 O− + CH3 I 
→ C6 Hl5OCH3 + I− C2 H 5 OH
51. (c)
Al 2 O 3 C2 H 4 + H 2 O
43. (c) C2 H 5 OH 
NaOH / I2
→ CHI3 (yellow ppt) o
Iodoform test 250 C Ethene
CH 3 OH 
→ No pptNaOH / I2

52. (a) Azeotropic distillation method –

44. (c) Phenol has higher boiling point than toluene because
Rectified spirit + Benzene + water
of hydrogen bonding.
↓ Fractional distillation
CH2 CH3 CH3
|| || | First fraction at 331.8 K is ternary azeotrope
45. (c) CH 3 OH 
NaOH
→ CH → CH − I →
HI
CH
I2 | | − I2 || ( H 2 O 7.4% + Benzene 74% + alcohol 18.5%)
CH2 −I CH2 −I CH2
Second fraction 341.2 K is a binary azeotrope
46. (b) Glycerol undergoes extensive hydrogen bonding due (Benzene 67.7% + Alcohol 32.2%)
to the presence of 3 –OH groups. As a result the glycerol Last fraction at 351K is absolute alcohol.
molecules are highly associated and thus it has high 53. (c) Benzyl alcohol and cyclohexanol are not acidic while
viscosity. phenol and m-chlorophenol are acidic due to presence of
Anhyd. ZnCl + HCl electron withdrawing groups like − NO 2 , − Cl, − CN
47. (c) (CH 3 )3 C − OH + HCl →
2

increases the acidic character of phenols. Hence, m-

(CH 3 )3 C − Cl + H 2 O 3° reacts immediately chlorophenol is more acidic than phenol.
(CH 3 )3 CH − OH + HCl →
2
Anhyd. ZnCl + HCl 54. (a) Phenols are much more acidic than alcohols but less so
than carboxylic acids or even carbonic acid. This is
(CH 3 ) 2 CH − Cl + H 2 O 2° reacts after 5 min.
indicated by the values of ionisation constants. The
Anhyd. ZnCl + HCl relative acidity follows the order:
CH 3 CH 2 CH 2 − OH + HCl →
2

CH 3 CH 2 CH 2 − Cl + H 2 O 1° reacts only on heating. Ka 10 −5 > 10 −7 > 10 −10 > 10 −14 > 10 −18
RCOOH H 2CO3 C6H5OH HOH ROH
55. (a) Glycerol 
HNO
→ Glyceryl trinitrate →
3 Absorbed on
Dynamite Assertion and Reason
Kieselguhr
+ 71. (a) It is correct that phenol is more reactive than benzene.
Glyceryl dinitrate
72. (c) It is correct that sodium phenoxide (sodium salt of
56. (d) Glucose 
Zymase
→ 2C 2 H 5 OH + 2CO 2
(From yeast) phenol) and CO2on heating from sodium salicylate. This
57. (c) Denaturing can also be done by adding 0.5% pyridine, is known as Kolbe’s reaction. Ethanol does not respond to
petroleum naptha, CuSO 4 etc. this reaction. Therefore, assertion is true. But the reason
that phenoxide ion is more basic than ethoxide ion is not
58. (b) A mixture of glyceryl trinitrate and glyceryl dinitrate correct.
when absorbed on kieselgurh is called dynamite.
73. (c) Lucas reagent is a mixture of anhydrous ZnCl 2 and
59. (a) C3 H 7 COOC 2 H 5 
Na / C2 H5 OH
→ C3 H 7 CH 2 OH
Ethyl butyrate Butyl alcohol
coc. HCl is used for the distinction of monohydric
60. (a) Glycol is used as an antifreeze for automobile radiators alcohol. Tertiary alcohols on addition produce a
because it lowers down the melting point of water. precipitate immediately while secondary alcohols
produce ppt. after 5 minutes. Primary alcohols do not
NCERT Exemplar Problems produce any precipitate. Therefore, assertion is true but
More than One Answer reason is false.
61. (b,c) CH 2 == CH 2 + H 2 O + [O] →
alk. KMnO 4
CH 2 — CH 2 74. (a) Phenols on treatment with neutral FeCl3 solution
| |
OH OH produce purple colour, resorcinol contains phenolic group
Glycol
hence in treatment with FeCl3 solution it gives purple
CH 2 == CH 2 + H 2 O 
Conc. H 2SO4
→ CH 3 — CH 2 — OH
Ethene Ethanol colour. Here both assertion and reason are correct and
reason is a correct explanation of assertion.
62. (a,d) —O — CH 2 — + HI 
→ +
75. (a) C 6 H 5 CH 2 OCH 3 →
H
C 6 H 5 CH 2+ + CH 3 OH
−

—OH +
Phenol does not react further with HI.
63. (a, b, c) X have two stereoisomers, All stereomers of X
have the same melting point, X reaction with SOCl 2
followed by alcoholic KOH product E which containing
8π bonds
64. (a, c) CH3CH 2CH 2 CH 2 OH , (CH 3 ) 2 CHCH 2 OH
65. (b, c, d) Reacting methane with steam at 900°C with a Ni
catalyst, Reducing formaldehyde with lithium aluminium
hydride,Reacting formaldehyde with aqueous sodium
hydroxide solution
CH2I 
I
→ C 6 H 7 CH 2 I
This can be explained on the basis of SN1 mechanism.
The carbonium ion produced being benzylium ion. Since
this type is more stable than alkylium ion.
76. (c) Lower the value of pKa, more acidic will be the
compound. Acetic acid is more acidic than phenol. This
indicates that carboxylate ion should be more stable than
the phenoxide ion and it is clear that carboxylate ion has
more equivalent resonating structures than the phenoxide
ion.
77. (a) The conversion of sugar into ethyl alcohol by yeast is
called alcoholic fermentation.

66. (b, c, d) HCl/anhyd. ZnCl 2 ,Victor-Meyer test,oxidation C12 H 22 O11 + H 2O 

Invertase
→ C6 H12O6 + C6 H12 O6
Glucose Fructose
with Cu at 573 K C6 H12O6 → 2C2 H5OH+ 2CO2
Zymase

67. (a, c) acetic acid,p-nitrophenol Ethyl alcohol

68. (a, b) Reacting sodium phenoxide with methyl chloride,
Reacting phenol with diazomethane (CH 2 N 2 )
69. (b) Carbinol is CH 3 OH (Methanol).
70. (a) Methanol is also referred as wood alcohol or wood
spirit or wood naphtha as the earliest method for its
preparation was by destructive distillation of wood.
78. (e) The dehydration of t-butanol involves the formation
of 3º carbocation which is more stable than 1º carbocation
in n-butanol. Thus, tendency to lose water becomes more
in t-butanol.
79. (c) A mixture of conc. HCl + anhyd. ZnCl 2 is called Lucas
reagent.
80. (e) The ease of dehydration of alcohols can be explained CH2 + I2 
→ Cl2 
OH−
→ C(OH)2 
→ C == O
on the basis of stability of the intermediate carbocation.
Greater the stability of the carbonation formed; greater 90. (b) 1-cycloethanol will give iodoform reaction.
will be the rate of reaction. The order of stability of 91. (a) CH 2 == CH ⋅ CH ⋅ CH 3 →
I
CH 2 == CH ⋅ CO ⋅ CH 3
2
[O ]
carbocation formed is |
OH
CH 3 CH 3 H But-3-en-2-ol
| | |
CH 3 — C +
H 3C — C +
CH3 — C+ CH 2 == CHCOCH3 
I2
→ CH 2 == CH ⋅ CO ⋅ CI3
| | |
CH 3 H H CH3 == CHCOCI3 
NaOH
→ CH 2 == CHCOONa + CHI3
This is due to the electron releasing (+I) effect of the alkyl
Match the Column
group. Therefore the ease of dehydration of alcohols 92. (b) A→2; B→5; C→4; D→1; E→3
follows the order.
Tertiary > secondary > primary alcohol. 93. (b) A→1; B→2; C→4; D→5; E→3

81. (c) Benzoylation in phenols is usually carried out in the 94. (d) A→2; B→3; C→4; D→5; E→1
presence of aqueous NaOH because benzoyl chloride is 95. (c) A→2; B→4; C→1; D→3; E→5
not readily hydrolysed by alkalies.
Integer
82. (b) Nitrous acid gives nitrosomine ion (NO+) which attacks
Molecular mass 46
phenol at less hindered p-position of form p-nitrosophenol 96. (23) Vapour density = = = 23
which is a tautomer of p-benzoquinone monoxide. 2 2

⇀
97. (10) 22400 ml of H 2 is produced by 46 gms of ethanol.
HO N=O ↽

O NOH
46 × 200 23
200 ml of H 2 is produced by =
p-Nitrosophenol p-Benzoquinone monoxime 22400 56
23
Percentage of C2 H 5 OH = × 100 = 9.6% ≃ 10%
83. (c) Nucleophilic attack of phenolate ion through the ortho- 56 × 10
carbon atom occurs on CCl 4 to form an intermediate 98. (3) Three, these are
which on hydrolysis gives salicylic acid. CH 3 CH 2 OCH 2 CH 3 (I), CH 3 OCH 2 CH 2 CH 3 (II)
84. (b) Depending upon whether the alkyl halide and the And CH 3 OCH(CH 3 ) 2 (III). Here I and II, I and III
alkoxide ion carry the same or different alkyl groups both are pairs of metamers.
symmetrical and unsymmetrical ethers can be prepared by
99. (10.22)
Williamsons synthesis.
OH OH
85. (d) (CH3 )3 CONa and CH 3CH 2 Br react to form Br
(CH 3 )3 C − O − CH 2 CH 3 . Good yields of ethers are obtained + 3 Br2 + 3 HBr
when primary alkyl halides are treated with alkoxides
derived from any alcohol. 1º, 2º or 3º. Br
1 mole 3 moles 1 mole
Comprehension Based
94 grams of phenol reacts with 480 gms. of Br2 .
86. (d) These are facts.
480
87. (c) Rest all will form carbocation 2 gm. of phenol — × 2 = 10.22 gms.
94
88. (d) CH 3 — CH — CH — CH 3 has CH 3 — CHOH
| | | OH OH
CH 3 OH
Br Br
Unit responsible for iodoform reaction. 100. (3) + 3 Br2 + 3 HBr
89. (a) Both have H2C < group attached to electron with
drawing groups and thus H-atom of > CH2 ecome reactive Br
2,4,6-tribromophenol
and such a H2C < group is called reactive methylene gp.

***