Alcohol, Phenol and Ether: Points to remember for MCQ:

• 1o alcohol or 10 haloalkane always undergo substitution and always follow SN2 mechanism.
• 2o or 30 alcohol or haloalkane always undergo elimination and always follow SN1 mechanism (need always protic solvent).
• Phenol and Anisole both undergo electrophilic substitution only at ortho and para position due to + resonance/mesomeric effect.
• Nitrobenzene and acetophenone both undergo electrophilic substitution only at meta position due to (-) resonance effect.

• Allylic alcohols: In these alcohols, the —OH group is attached to a sp3 hybridised carbon next to the carbon-carbon double bond,
that is to an allylic carbon. Or you can say beta (ẞ)-carbon will be sp2 hybridised.

• Benzylic alcohols: In these alcohols, the —OH group is attached to a sp3—hybridised carbon atom next to an aromatic ring.

1|Page
 • Vinylic alcohols: when —OH group bonded to a carbon-carbon double bond. So, we can say phenol also vinylic.

• Hydration of alkene in presence of dil. Acid always gives alcohol according to Markownikov`s rule. Like (-2-ol)

• Hydration of alkene according to Hydroboration always gives alcohol according to Antimarkownikov`s rule. Like (-1-ol)
B2H6 / H2O2 /H2O / OH-
CH3-CH=CH2 CH3-CH2-CH2-OH

• Hydration of alkene in presence of dilute Acid follow three steps:

Step 1: Protonation of alkene to form carbocation by electrophilic attack of H3O+ .
Step 2: Nucleophilic attack of water on carbocation.
Step 3: Deprotonation to form an alcohol.
Practice some examples for hydration:

2|Page
 • Respective catalysts are reducing agent: like platinum, palladium, nickel , sodium borohydride (NaBH4) or lithium aluminum hydride
(LiAlH4) convert Aldehydes yield primary alcohols whereas ketones give secondary alcohols.
• Reduction of carboxylic acids and esters into primary alcohol only possible by lithium aluminum hydride, a strong reducing agent.

• Phenol, also known as carbolic acid.

• Alcohols act as nucleophiles when the bond between O–H is broken down.
• Alcohols act as electrophiles when the bond between C-O is broken down.

3|Page
 • Boiling point: Alcohol > Ether > Hydrocarbon
(H-Bonding) dipole-dipole Weak Dispersion forces

• Remember one thing boiling point depends upon following factors:

o High molar mass
o High surface area (if more branch is there in any isomeric structure, then less boiling point due to less surface area.)
o High Vander Waals forces
o H- bonding
Practice some examples
1. Formula CH3(CH2)3CH3 C2H5-O-C2H5 CH3(CH2)3-OH
n-Pentane Ethoxyethane Butan-1-ol
b.p./K 309.1 307.6 390

2. Pentan-1-ol, butan-1-ol, butan-2-ol, ethanol, propan-1-ol, methanol.

3. Pentan-1-ol, n-butane, pentanal, ethoxyethane.

Q: Propanol has higher boiling point than that of the hydrocarbon, butane: due to hydrogen bonding.

4|Page
 • Reactivity of alcohol: 10 < 20 < 30 (reactivity depends upon the stability of carbocation and 30 carbocation is more stable.)
• Reactivity of alcohol we can find out with the help of Lucas reagent (conc. HCl and ZnCl2)
• With Lucas reagent :
30 – Gives turbidity immediately
20- Gives turbidity within 5-minutes
10- Do not give turbidity at room temperature
• Alkoxide ion(RO─) is a better proton acceptor than hydroxide ion, which suggests that alkoxides are stronger bases.
• Alkoxide ion(RO─) and Hydroxide ion(HO─) both are negatively charged so we feel they always act as nucleophile but its not true in
some case they behave like stronger base.

With 10 haloalkane Types of reaction Mechanism With 20 or 30 Type of reaction Mechanism

or alcohol haloalkane or alcohol

Alkoxide ions (RO─) Nucleophile Substitution SN2 Stronger base Elimination SN1

Hydroxide ion(HO─) Nucleophile Substitution SN2 Nucleophile Substitution SN2

5|Page
 ❖ Primary and secondary alcohol can undergo oxidation, but Tertiary
alcohols do not undergo oxidation reaction, tertiary alcohols always undergo
dehydration to give alkene .

• How we can distinguish phenol:

• (i) phenol gives violet colour with FeCl3.
• (ii) Phenol gives white ppt with liquid bromine

6|Page
 • Williamsons synthesis help in ether formation: R—X + Na—O— R—O— + NaX
• In Williamson`s synthesis: haloalkane should be 10 to go for formation of ether through substitution. Eg:

• Limitation In Williamson`s synthesis: If haloalkane is 20 or 30 then formation of alkene takes place through elimination. Eg:

Question: The following is not an appropriate reaction for the preparation of t-butyl ethyl ether.
CH3 CH3

H3C C Cl + H3C CH2 O Na H3C C O CH2 CH3

CH3 CH3

2-chloro-2-methylpropane 2-Ethoxy-2-methylpropane

(i) What would be the major product of this reaction. (ii) Write a suitable reaction for the preparation of t-butyl ethyl ether
Ans) (i) The major product of the given reaction is 2-methylprop-1-ene. It is because sodium ethoxide is a strong nucleophile as well as
a strong base. Thus, elimination reaction predominates over substitution.

CH3 CH3

(ii) H3C C O Na + H3C CH2 Cl H3C C O CH2 CH3

CH3 CH3
2-Ethoxy-2-methylpropane

7|Page
 1. Bond angle in alcohols (109o) is slightly less than the tetrahedral angle (109°-28`) but bond angle in ether is slightly greater
than the tetrahedral angle: :

O O
R H R R

in alcohol lone pair bond pair in ether repulsion between alkyl group is
repulsion is greater than alkyl and more than lone pair bond pair repulsion
hydrogen atom repulsion

2. Ethers possess a net dipole moment even if they are symmetrical in structure?
Because, due to greater electronegativity of O- atom carbon C – O bonds are polar and C – O bond are inclined to each other at an
angle of 110° (or more), so, two dipoles do not cancel out each other.
3. Carbon– oxygen bond length (136 pm) in phenol is slightly less than that in CH3OH:

(i) partial double bond character because of the conjugation of unshared electron pair of oxygen with the aromatic ring
(ii) sp2 hybridised state of carbon to which oxygen is attached.
8|Page
 4. Commercially preparation of alcohol: acids are reduced to alcohols by converting them to the esters followed by their reduction
using hydrogen in the presence of catalyst (catalytic hydrogenation).

Explain Esterification:

5. Water is removed as soon as it is formed in esterification: b`cos of auto catalysis nature of H2O which make the reaction reverse
and therefore, water is removed as soon as it is formed.
6. In esterification if we have used acid chloride instead of acid anhydride then we add pyridine a base. Because: The reaction
with acid chloride is carried out in the presence of a base (pyridine) to neutralise HCl which is formed during the reaction. It shifts
the equilibrium to the right-hand side. (Otherwise, HCl reverse the reaction in backward direction by providing its H+).
Pyridine as a base
RCOC + R `OH ⎯⎯⎯⎯⎯⎯⎯⎯→ RCOOR ` + HC
Acid Chloride Alcohol Ester Strong acid
7. Acetyl chloride and acetic anhydride are often used instead of acetic acid b`cos they are more reactive and give better yields of product.
8. Alcohols are comparatively more soluble in water than hydrocarbons of comparable molar masses: due to H-bonding
9|Page
 Topic : Acidic Strength
• pKa value is inversely proportional to acidic
strength.
• Electron withdrawing group:(EWG)
like NO2, Halogens (F, Cl, Br, I ) etc.
Increase the acidic nature of phenol.
• Electron donating group: (EDG)
like Alkyl (CH3-, C2H5-), Alkoxy etc.
Decrease the acidic nature of Phenol.
•

• Arrange according to acidic strength:

p-Nitrophenol > o-Nitrophenol > m-Nitrophenol > phenol > m-Cresol > o-Cresol= p-Cresol > Ethanol

9. Acidic strength of alcohol follows the given Order: 1o > 2o > 3 o

10. Acidic nature of phenols more than alcohol:

➢ phenoxide ion is more stable due to presence of resonance whereas, alkoxide ion is less stable due to absence of resonance.
➢ Phenol gives litmus paper test whereas alcohol do not gives litmus paper test.
11. Alcohols are weaker acid then water: water is a better proton donor (i.e., stronger acid) than alcohol. Also, in the below reaction,
we note that an alkoxide ion is a better proton acceptor( conjugate base) than hydroxide ion.
-
2RO + H 2 O ⎯⎯ → 2R-OH + OH-
Base Acid C. acid C. Base
10 | P a g e
 12. Condition for dehydration of alcohol into alkene: Follow SN1 Mechanism when the alcohol is 2o or 3o which gives alkenes.

Conc. H2SO4 / 443K

1o Alcohol Butan-1-ol gives but-2-ene due to hydride shifting

2oAlcohol 80% Conc. H3PO4 /440K

Alkene

3o Alcohol 20% Conc.H3PO4/358K

13. o-Nitrophenol is highly steam volatile and has low boiling point : due to intramolecular hydrogen bonding
14. p-nitrophenol is less volatile and high boiling point: due to intermolecular hydrogen bonding
15. denaturation of alcohols means: The commercial alcohol is made unfit for drinking by mixing in it some copper sulphate (to give it
a colour) and pyridine (a foul-smelling liquid). It is known as denaturation of alcohol.
16. Formation of ether from alcohol: is a nucleophilic bimolecular SN2 reaction.
17. Preparation of ethers by acid dehydration of secondary or tertiary alcohols is not a suitable method. Give reason.

ANS. The formation of ethers by dehydration of alcohol is a bimolecular reaction SN 2 so alkyl group should be unhindered. In case
of secondary or tertiary alcohols, the alkyl group is hindered. As a result, elimination dominates substitution.
18. Phenols do not give protonation reactions readily. (Protonated means those can give electron(LONE PAIR) to accept H+ ion)
ANS. The lone pair on oxygen of –OH in phenol is being shared with benzene ring through resonance. Thus, lone pair is not fully
present on oxygen and hence phenols do not undergo protonation reactions.
19. Phenol, is more easily nitrated as compared to benzene why?

Ans. Nitration is an electrophilic substitution. The –OH group in phenol increases the electron density at ortho and para position as
follows Since phenol has higher electron density due to electron releasing nature of -OH group , compared to benzene , therefore
nitration is easy in phenol than benzene.
11 | P a g e
 20. Which alcohol is known as ‘wood spirit’: Ans: Methanol, CH3OH, is known as ‘wood spirit’,
21. Grignard reagent(R-MgX):

HCHO(Methanal): always gives 10 Alcohol (R-CH2OH)

Any aldehyde other than Methanal: always gives 20 Alcohol
Any ketone: always gives 30 Alcohol.

12 | P a g e
 22. Write the structures of the major products expected from the following reactions:
(a) Mononitration of 3-Methylphenol (b) Dinitration of 3-Methylphenol (c) Mononitration of phenyl Ethanoate.

23. Commercial preparation of ethanol: The sugar in molasses, sugarcane or fruits such as grapes is converted to glucose and fructose, (both
of which have the formula C6H12O6), in the presence of an enzyme, invertase. Glucose and fructose undergo fermentation in the presence of
another enzyme, zymase, which is found in yeast. Fermentation takes place in anaerobic conditions i.e. in absence of air. Carbon dioxide is
released during fermentation. The action of zymase is inhibited once the percentage of alcohol formed exceeds 14 percent. If air gets into
fermentation mixture, the oxygen of air oxidises ethanol to ethanoic acid which in turn destroys the taste of alcoholic drinks.

(Markownikov rule) Hydration: Addition of water

Alkene to Alcohol: Ethene to Ethanol, Propene to Propan-2-ol
Dil H2SO4 with H2O
OH
Or CH3-CH=CH3
H+ / H2O
CH 3-CH-CH3
(H+/H2O) Propene Propan-2-ol

(Antimarkownikov`s) B2H6 / H2O2

Hydroboration Reaction CH3-CH=CH3 CH3-CH2-CH2-OH
-
B2H6/ H2O2/ OH─/ H2O Propene H2O/ OH Propan-1-ol

Dehydrating agent: Dehydration: Removal of water

a. Conc. H2SO4 /443K 1oAlcohol → Alkene
b. H3PO4 conc. H2SO4
c. anhydrous ZnCl2 CH3CH2-CH2-OH 443K CH3-CH=CH2
d. Alumina (Al2O3) Propan-1-ol Propene
e. P2O5/ heat

13 | P a g e
 O
Cl O Na
Na2Cr2O7 /dil H2SO4
NaOH / 623K dil HCI
Oxidation
320atm
Jitender O
Chlorobenzene sodium phenoxide sir p- Benzoquinone
OH OH
Br
Br2/CS 2 / 273K
NH2 N=N-CI OH organic solvent +
Br
NaNO2/HCI H2O p-Bromophenol o- Bromophenol
273-278K Warm
OH
Aniline BDC Br
phenol Br
Br2 / H 2O
SO3H aqueous
Br
H2S2O7 NaOH 2,4,6-Tribromophenol
+
oleum H NO2 OH NO2
(Benzenesulphonic acid)
Conc. HNO 3

OH
H3C CH3 O NO2
H3C CH3
2,4,6-Trinitophenol

O2 H+ OH OH
H2O NO2
aerial oxidation dil.HNO 3
Cumene +
Cumenehydroperoxide

NO2 o-Nitrophenol
Intramolecular H-bond)
p-Nitrophenol
( Intermolecular H- bond) (Low B.pt. / More volatile)

Jitender (High B.pt.) / less volatile

Best of Luck sir
OH OCOCH3
COOH
+
NaOH/CO2/H
(CH3CO)2
COOH
kolbe`s reaction H+
Salicylic acid (Aspirin)
Acetylsalicylic acid
OH
+ CHO
CHCI3/NaOH/H
Reimer tiemann
Salicyldehyde
OH

14 | P a g e CH3COCI / Anhyd. AICI3 + ortho isomer

Friedel craft acylation also
COCH3
p- Hydroxy acetophenone
 Practice for alcohol / phenol conversion:

15 | P a g e
16 | P a g e
17 | P a g e