15.

Alcohols, Phenols and Ethers

Alcohols: Hydroxy derivatives of hydrocarbons

Alcohols

Aliphatic alcohols Aromatic alcohols

Monohydric (CnH2n+1OH) ( OH group is present
in side chain of aromatic ring)
* Alcohol having one OH group
CH2 OH
Ex: CH3 CH2 OH
Dihydric (CnH2n(OH)2)
* Alcohol having two OH group benzyl alcohol
Ex: OH OH
CH2 CH2 glycol
Trihydric (CnH2n+1(OH)3)
* Alcohol having three OH group
Ex: CH2 OH
CH OH
CH2 OH glycerol

Classification of monohydric alcohols

(i) Compounds containing CSp3 − OH
Alkyl alcohol
( OH group attached to sp3 Carbon atom)

o
Primary alcohol (1°) Secondary alcohol (2 ) Tertiary alcohol (3o)
* OH CH3
CH2 CH2 OH
CH3 CH CH3 CH3 C* OH
*
CH3
Allylic alcohol
( OH group attached to sp3 Carbon adjacent to C C bond)

1° allylic 2o allylic 3o allylic

CH2 CH CH * OH CH3 CH3
2
CH2 CH CH OH CH2 CH C* OH
*
CH3

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2ME2324C(NRP-Summary sheet)

Benzylic alcohols
( OH group attached to sp3 carbon atom next to an aromatic ring)

o o
1 benzylic 2 benzylic o
3 benzylic
*
CH CH3
2 OH CH3
CH2 OH *C OH
*
CH3
(ii) Compounds containing C2 − OH : These alcohols Contain –OH group attached to carbon–carbon double
sp

bond
Ex: CH2 = CH – OH Vinylic alcohol

Phenols Classification:
The –OH group is directly
Bonded to benzene ring

Monohydric Dihydric Trihydric

CH3 OH OH
OH OH

OH
O Cresol Catechol
OH
hydroxy quinol
CH3 OH OH

OH OH OH OH
m-Cresol Resorcinol Phloroglucinol

CH3 OH CH3
OH

OH
OH Pyrogallol
OH
p-Cresol Quinol

Ethers:
Alkoxyalkanes

Simple | Symmertical (alkyl or aryl group attached

(alkyl or aryl group attached to to oxygen are different)
oxygen are same) R O R1
R O R

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 2ME2324C(NRP-Summary sheet)

Structure of functional group

Alcohol Phenol Ether
142 pm 141 pm
:O:
:O: H :O:
H3C H 109o H3C CH3
111.7 o
108.9o 136 pm

• Bonding angle in alcohol and phenol is slightly less than 109.281 due to repulsion between lone pairs
• Bond angle in ether is greater than 109.281 due to repulsion between bulky alkyl groups
• Bond angle order Methoxy methane > Phenol > Methanol
• Bond length (C  O) methanol > methoxy methane > Phenol.
• Bond length of C–O bond is shortest in Phenol due to conjugation of lone pairs of oxygen with the
aromatic ring (Partial double bond nature).
Preparation of alcohol
(i) From alkenes:
OH
H2 O | H+
(Propan-2-Ol)
(Electrophilic addiation takes place
according to markovnikov Rule]

i) B2H6 OH (Propan-1-Ol)
ii) H2O, H2O2, OH
[Hydroboration-oxidation, looks like addition of
water in anti-markovnikov fashion]

From Carbonyl compounds

(i) Reduction of aldehyde or ketone
O
H2 | Pt or Pd or Ni
R C H R CH2OH
OR
o
Aldehyde NaBH4 | CH3OH 1 Alcohol
OR
LiAlH4 | H2O
O OH
Reducing agent
R C R R CH R
2o Alcohol
(ii) Reduction of acid and ester
O
LiAl H4| H2O
R C OH R CH2 OH
or B2H6 | H2O
O
H2, pt
R C OR1 RCH2OH+R1OH
(Catalytic Hydrogenation)

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2ME2324C(NRP-Summary sheet)

• As LiAlH4 is an expensive reagent, therefore acids are converted to ester and then reduced by catalytic
hydrogenation.

From Grignard reagents

O
H2O
RMgX + H C H R CH2 OMgX R CH2OH + Mg(OH)X
Formaldehyde 1° alcohol
O
R1 C H H2O
R CH OMgX R CH2 R1+Mg(OH)X
(any other aldehyde)
2o alcohol
R1
O
OMgX OH
R1 C R1 H 2O
R C R1 R C R1 + Mg(OH)X
(Ketone)
R1 R1
3° alcohol

Phenol Preparation
Cl ONa OH
Cl2 NaOH HCl
anhydrous 623 K, 300 atm
AlCl3

SO3H OH
oleum i) NaOH.∆
ii) H+

NO2 NH2 N2 Cl OH
conc.HNO3 Sn|HCl NaNO2 H2O
+ N2 + HCl
H2SO4 HCl warm
(0 – 5 °C)
CH3 CH3
CH CH3 H3C C O O H
OH
CH3CH2 CH2Cl O2
H+ + CH3COCH3
Anhyd. AlCl3 368-408 K 323-363 K, H2O acetone
Cumene Cumene
(Isoprophylbenzene) hydroperoxide

Physical Properties: Alcohols, Phenols and ethers

Boiling point: –OH graph is alcohol and phenols is involved in intermolecular hydrogen boning which is
absent in ethers. Therefore, they have higher boiling point than hydrocarbons, ethers, haloalkanes and
haloarenes of comparable molecular mass.
CH3CH2OH CH3OCH3 CH3CH2CH3
351 K 248 K 231 K
CH3CH2CH2CH2OH C2H5OC2H5 CH3CH2CH2CH2CH3
390 K 307.6 K 309.1 K
• Large difference in boiling point of alcohol and ethers is due to presence of H-bonding in alcohols.

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 2ME2324C(NRP-Summary sheet)

Solubility
• They are soluble in water due to their ability to form H-bond with water.
• Solubility decreases with increase in molecular mass
• Several lower, molecular mass alcohols are miscible with water in all proportions
• Alcohols and ethers have almost close miscibility, Butanol 7.5g | 100 ml and 9 g| 100 ml for ethoxy
ethane

Acidic nature of alcohols: Alcohols have polar O – H bond

• Acidic nature can be explained on the release of proton due to cleavage of O – H bond. Tertiary alcohols
are least acidic as the +I effect of alkyl groups is maximum and makes release of proton difficult. As +I
effect increase electron density on oxygen decreases hence the polarity of O – H bond decreases. Thus
order of acidity is:
CH3OH > Primary > Secondary > Tertiary
• Alcohols are weaker acids than water. Alkoxide ion is stronger base than OH– ion

Acidic Nature of Phenol

• Phenol is a stronger acid than alcohols but weaker than carboxylic acids. Its acidic nature is due to the
formation of a resonance stabilised phenoxide ion.

• The delocalisation of negative charge throughout the ring is the main stabilising factor.
• Resonance structures also explain the ortho and para directive influence of the –OH group.
• No such resonance is possible for the alkoxide ion, RO–, where the negative charge remains on the
oxygen atom only, therefore alcohols are less acidic.

Effect of substituents on acidity of phenols

• Presence of electron withdrawing groups (–NO2, –Cl, –CN, –COOH, –CHO, etc.) on the benzene ring
increases the acidity of phenol as it facilitates the release of proton.
• The effect is greater for the substituents are at o-or p-positions than at m-position, e.g. the order of acidic
strength: p-nitrophenol > o-nitrophenol > m-nitrophenol > phenol.
• Presence of electron donating groups (– CH3, – OCH3, etc.) on the benzene ring decreases the acidity as
it strengthens the negative charge on oxygen atom thereby making the release of proton difficult.
• Cresols are therefore less acidic than phenols, but m-methoxy and m-amino phenols are stronger acids
than phenol due to –I effect and absence of +R effect, e.g. the acidic order:
phenol > m-cresol > p-cresol > o-cresol
Acidic order for chloro phenols follows the order o– > m – > p– and for dihydric phenols: m– > p– > o–
• Greater values of Ka or lower values of pKα indicate a stronger acid.
• Acidic nature of phenol is supported by its reaction with highly electropositive metals and strong
alkalies.

5
2ME2324C(NRP-Summary sheet)

e.g. 2C6 H 5OH + 2Na 

→ 2C6 H 5 ONa + H 2
C6 H 5 OH + NaOH 
→ C6 H 5 ONa + H 2 O
Sodium phenoxide

• Phenol does not react with sodium carbonate or bicarbonate to liberate carbon dioxide as it is a weaker
acid than carbonic acid.

Reactions of Alcohols

Na, NaH
CH3CH2ONa + 1 H2 (indicate acidic nature of alcohol)
Sodium ethoxide 2
CH3COOH, H+
CH3COOC2H5 + H2O (Reaction is reversible, therefore water is removed
Esterification Ethyl ethanoate
as soon formed to drive the reaction)
CH3COCl
Pyridine
CH3COOC2H5 +HCl [Pyridine is used to neutralise HCl formed]
Ethyl ethanoate
RMgX
conc. anhydrous
CH 3CH2OMgX + RH
Alkane
HCl/ZnCl2
CH3CH2Cl [Mixture of conc HCl: anhydrous ZnCl2 is called Lucas reagent,
Chloroethane order of reactivity: 3° alcohol > 2° > 1°]
PCl5
CH3CH2Cl [SNR]
Chloroethane
KBr, H3PO4 [SNR]
CH3CH2Br
Bromoethane
KI, H2SO4 [SNR]
CH3CH2I
CH3CH2OH
Iodoethane
Ethanol PX3 or (P + X)2
CH3CH2X (X = Br, I) [SNR]
Haloalkane
SOCl2
CH3CH2Cl [SNR]
Pyridine
Chloroethane

[O] CH3COOH [with strong oxidising agent like KMnO4, K2Cr2O7]

Ethanoic acid * with PCC and CrO3, 1° alcohol → aldehyde, 2° → ketone, 3°→ no reaction

Cu, 573 K [1° alcohol → aldehyde, 2° alcohol-Ketone and 3° alcohol-alkene]

CH3CHO
Dehydrogenation Ethanal
383 K
C2H5HSO4
Ethyl hydrogen
sulphate
H2SO4 413 K
C2H5OC2H5
Dehydration Diethyl ether
443 K
CH2 CH2
Ethene
85% H3PO4
2o alcohol alkene

o 20% H3PO4
3 alcohol alkene (order of reactivity 3° > 2° > 1°)

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 2ME2324C(NRP-Summary sheet)

Reactions of Phenols
OH

1) NaOH COOH
2) CO2
(Kolbe's reaction)
3) H+
Salicylic acid
ONa ONa OH
CHCl3 CHCl2 NaOH CHO H+ CHO
NaOH(aq)

(* Reimer - Tiemann reaction) Salicylic acid

Na, NaOH + H2 (acidic nature)
C6H5ONa
Sodium phenoxide
Zn
C6H6 (Reduction)
Benzene
NH3 (SN Ar)
C6H5NH2
ZnCl2/Distil
Aniline
CH3COCl
or (CH3CO)2O C6H5OCOCH3 (Acetylation)
Phenyl acetate
C6H5COCl
C6H5OCOC6H5 (Benzoylation)
Phenyl benzoate
OH
OH OH
Br
Br2, CS2
+ (Electrophilic aromatic substitution)
293 K
Phenol SEAr
Br
o-Bromophenol p-Bromophenol
OH
Br2 (aq) Br Br
(SEAr Test for phenol)

Br
2,4,6-Tribromophenol (white ppt.)
OH OH

dil. HNO3
NO2
+ [Separated by steam distillation O-nitro phenol
298 K
steam volatile due to intramolecular H-bonding]
NO2
o-nitrophenol p-nitrophenol
OH
NO2 NO2
HNO3
H2SO4

NO2
Picric acid (poor yield)
OH
conc H2SO4 SO3H conc. HNO3
288-293 K picric acid

SO3H
Phenol-2,4-disulphonic acid
O

Na2Cr2O7/H2SO4

O
Benzoquinone

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2ME2324C(NRP-Summary sheet)

Ethers
Ethers are called alkoxy alkanes.

Williamson’s synthesis

R' O Na + X R R' O R

CH 3CH 2 ONa + BrCH 2 CH3 

→ CH3CH 2 OCH 2 CH3 + NaBr
 Reaction involve SN2 attack of alkoxide ion on alkyl halides
 In case 2° and 3° alkyl halides are used, elimination competes.
 3° alkyl halide lead to formation of alkene (elimination)
 Phenyl ethers are synthesized by phenoxide ion reaction with 1° RX
 Both symmetrical and unsymmetrical ethers can be synthesized.

Dehydration of alcohols
• CH 3CH 2 OH 
Conc.H 2 SO4
413 K
→ CH3CH 2 OCH 2 CH3
Ethoxyethane

 Suitable for preparation of ethers having primary alkyl group, alkyl group should be unhindered (1°)
and temperature kept low.
 Suitable for preparation of symmetric ethers.
Reactions Hydrolysis
H+
ROR + H 2 O  → 2ROH
Reactions with HX
R − O − R1 + HX 
373 K
→ R − OH + R1x(If R1 < R)
OCH3 OH

+ HI + CH3I

Anisole
• In alkyl aryl ethers, the products are always phenol and alkyl halide, and never an aryl halide and
alcohol.
• In case of 3° alkyl ethers, 3° alkyl group is converted to halide and other alkyl group to alcohol.
• Order of reactivity HI > HBr > HCl
• Diethyl ethers such as diphenyl ethers are not cleaved by HI.
CH 3CH 2 OCH 2 CH 3 dil. H 2SO4
→ 2CH3CH 2 OH
PCl5 , ∆
CH 3CH 2 OCH 2 CH 3  → 2CH3CH 2 Cl + POCl3

8
 2ME2324C(NRP-Summary sheet)

Electrophilic substitution
Alkoxy group is o- and p-directing group in electrophilic substitution reactions.
Reactant Conditions Products
OCH3 OCH3
OCH3 Br
+

→ Br2 in
Ethanoic acid
Br o-Bromoanisole
p-Bromoanisole (Minor)
Anisole (Major)
OCH3 OCH3 OCH3
CH3
+
+ 2CH3Cl

Anhyd. AlCl3
CS2
→ 2-Methoxytoluene
methyl (Minor) CH3
Anisole 4-Methoxytoluene
chloride
(Major)

• Friedel-Craft’s alkylation
OCH3 OCH3 OCH3
COCH3
+ 2CH3COCl +
acetyl chloride 
Anhyd. AlCl3
→ 2-Methoxy-
Anisole acetophenone COCH3
(Minor) 4-Methoxy
acetophenone
(Major)

• Friedel-Craft’s acylation
OCH3 OCH3 OCH3
NO2
+

H 2SO4
HNO3
→ 2-Nitroanisole
(Minor) NO2
Anisole 4-Nitroanisole
(Major)

Order of reactivity towards electrophilic substitution reaction:

Haloarenes < Toluene < Anisole < Phenols

Commercially important alcohols

Preparation:
Methanol is called wood spirit as it was obtained by the destructive distillation of wood. It is manufactured
by passing a mixture of carbon monoxide and hydrogen over a preheated catalyst at 600 K under pressure.
(CuO.ZnO.Cr2O3)
[CO + 2H2] CH3OH
200 - 300 atm; 573 - 673 K
Water gas [CO + H2] is source for carbon monoxide and hydrogen.

Ethanol (ethyl alcohol) CH3CH2OH

Preparation: From molasses
C12 H 22 O11 + H 2 O 
invertase
yeast
→ C6 H12 O6 + C6 H12 O6
( Sucrose ) ( glucose ) ( fructose )

C6 H12 O6 → 2C2 H5 OH + 2CO 2 ↑

zymase

( glucose ) / ( fructose )

9
2ME2324C(NRP-Summary sheet)

A dilute solution (7% - 10%) of ethanol called wash is obtained. It is subjected for fractional distillation to
get rectified spirit (95.5% ethanol).
From ethene: Ethene is passed into concentrated sulphuric acid at 350 K and 30 atm, ethylhydrogen
sulphate is formed.
CH 2 = CH 2 + H 2SO4 + H 2O →
350K/30atm
CH3CH 2 HSO 4
Hydrolysis of ethylhydrogen sulphate gives ethanol and sulphuric acid.
CH3CH 2 HSO4 + H 2O  → CH3CH 2OH + H 2SO4
Fractional distillation of aqueous solution yields rectified spirit.

Denaturation of alcohol
Ethanol is mixed with methanol (poison), a little amount of pyridine (a foul smelling liquid) and CuSO4 to
make it unfit for drinking. This is called denaturation of alcohol. This sample is called denatured alcohol
also known as methylated spirit.

Sl. No. Keywords

1. Alcohols - Mono, Di, Tri or Polyhydric alcohols
2. Compounds containing Csp3 −OH bond - alkanols
3. Allylic alcohols
4. Benzylic alcohols
5. Compounds containing Csp2 −OH bond - Vinylic alcohol
6. Phenols-Mono, Di and Trihydric phenols
7. Ethers - Symmetrical ethers, Unsymmetrical or mixed ethers
8. Nomenclature - Alcohols, Phenols, Ethers
9. Common name
10. IUPAC name
11. Structures of Functional Groups - Bond angle, Bond length
12. Alcohols Preparation
13. By acid catalysed hydration of alkene
14. By hydroboration –oxidation of alkene
15. By reduction of aldehydes and ketones - catalytic hydrogenation, NaBH4, LiAlH4
16. By reduction of carboxylic acids - only LiAlH4
17. Esters - LiAlH4 and catalytic hydrogenation
18. From Grignard reagents
19. Preparation of Phenols
20. From haloarenes
21. From benzenesulphonic acid
22. From diazonium salts
23. From cumene
24. Physical properties - Boiling points, Solubility
25. Reactions involving cleavage of O − H bond
26. Reaction with metals

10
 2ME2324C(NRP-Summary sheet)

27. Acidity of alcohols - reason and order of acidic strength

28. Acidity of phenols - reason for higher acidity compare to alcohols
29. Effect of EDG and EWG on acidic strength of phenol
30. Esterification
31. Reaction with hydrogen halides – Lucas test
32. Reaction with phosphorus trihalides
33. Dehydration – Mechanism and order of reactivity
34. Oxidation - using mild oxidizing agent like PCC or CrO3
35. Oxidation - using strong oxidizing agent
36. Reaction of phenols - Electrophilic aromatic substitution
37. Nitration – with dilute and concentrated HNO3
38. Halogenation – with Br2/CS2 and Br2/H2O
39. Kolbe’s reaction
40. Reimer - Tiemann reaction
41. Reaction of phenol with zinc dust
42. Oxidation
43. Some Commercially Important Alcohols - Methanol, Ethanol
44. Denaturation of Ethanol
45. Preparation of ethers - By dehydration of alcohols
46. Williamson synthesis - general reaction and limitation
47. Physical properties - Boiling point
48. Cleavage of C − O bond in ethers – reaction with HI
49. Electrophilic substitution
50. Halogenation
51. Fridel-Crafts reaction
52. Nitration

Analysis of the chapter

Test Date / Number Comfortable To be revised Need clarity
NRP
CT
FLP
GT

***

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2ME2324C(NRP-Summary sheet)

− Space for Notes −

12