Alcohol, Phenol & Ether

Classification
(on the basic of number of hydroxyl Group)

Monohydric Dihydric Trihydric

(i) C2 H5 − OH (i) CH2 − OH (i) CH2 − OH
| |
OH
CH2 − OH CH − OH
(ii) |
(ii) OH
CH2 − OH
OH OH
(ii)
OH
OH
 Classification

‘OH’ is attached ‘OH’ is attached

to Sp3 carbon to Sp2 carbon
Normal Allylic Benzylic
Alcohol Alcohol Alcohol
−CH2 − OH CH2 = CH2 − OH CH2 OH
Primary (1°) Primary Allylic alcohol
1° Benzylic alcohol
Alcohol
OH CH3
CH2 = CH − CH − OH
C − OH | CH
CH3
Secondary (2°) Secondary allylic alcohol
Alcohol CH3
| 2° Benzylic alcohol
C − OH CH2 = CH − C H − OH CH3
| CH OH
Tertiary 5° CH3 CH3

Alcohol Tertiary allylic Alcohol

3° Benzylic alcohol
 Classification

‘OH’ is attached ‘OH’ is attached

to Sp3 carbon to Sp2 carbon

Phenol
Vinylic OH
Alcohol
CH2 = CH − OH
OH
CH3
 Common & IUPAC naming of Alcohol, Phenol & Ether

Compound Common Name IUPAC

(1) CH3OH

(2) CH3CH2OH

(3) CH3CH2CH2OH

(4) CH3 − CH − OH
|
CH3

(5) CH3CH2CH2CH2OH
 Compound Common Name IUPAC

(6) CH3 CH − CH2 − CH3

|
OH

(7) CH3 − CH − CH2 − OH

|
OH

CH3
|
(8) CH3 − C − OH
|
CH3

(9) CH2 − OH

CH2 − OH
 Compound Common Name IUPAC

(10) CH2 − CH − CH2

| | |
OH
OH OH

(11)
 Compound Common Name IUPAC

(13)

(14)

(15)
 Compound Common Name IUPAC

(16)

(17)
 Compound Common Name IUPAC

(18)

(19)
 Compound Common Name IUPAC

(20)

(21)

(22)
 Compound Common Name IUPAC

(23)

(24)
 Compound Common Name IUPAC

(25)

(26) CH3OCH3

(27) C2H5OC2H5

(28) CH3OC3H7
 Compound Common Name IUPAC
(29) C6H5OCH3

(30) C6H5OC2H5
General Method of preparation of Alcohol: - 8 Ways
(1) Alkane → Alcohol
𝐻+
Tertiary alkane tertiary alcohol
𝐾𝑀𝑛𝑂4

(2) Alkene → Alcohol

• Acid catalyzed hydration (stable carbocation & Rearrangement)
• Hydroboration – Oxidation (HBO)
• AMK Rule → No carbocation forms
• Syn addition of H & OH.
• OMDM (MK rule):-
• No rearrangement occurs
• Anti addition of H & OH
 SN1
(3) Alkyl halide → Alcohoal
SN 2
(4) Aldehyde / Ketone → alcohol (Reduction)
H2
(i) Catalytic hydrogenation
Ni:/pt/pd
(ii) L𝑖𝐴𝑙𝐻4 𝑜𝑟 𝑁𝑎𝐵𝐻4
(5) Carboxylic acid & derivative
(i) Reduction using LiAlH4 & NaBH4
(6) Grignard → alcohol
Nucleophilic addition
Nucleophilic addition elimination

(7) Ester → alcohol (Hydrolysis)

(8) Primary amine → alcohol (using diazonium salt)

 Alkane ⟶ Alcohol
(1) Alkane → Alcohol
𝐻 + /𝐾𝑀𝑛𝑂4
• Tertiary alkane Alcohol
(3°) Δ (3°)

CH3 CH3
| H+ /KMNO4 |
• CH3 − C − H CH3 C − OH
| [0] |
CH3 CH3
 Alkene ⟶ Alcohol
(2) From alkene: -
H+
(i) Acid Catalyzed hydration
H2 O
i BH3 /THF
(ii) HBO (Hydroboration oxidation)
2 H2 O2 /OH(−)
i Hg OAC 2 /H2 O
(iii) OMDM (oximes curation – demedication)
2 NaBH4
(i) ACID catalyzed Hydration:
• MK rule follow
• Carbocation form (Rearrangement occur)
• OH attacks
H⊕
• R − CH = CH2 𝑅 − CH − CH3
H2 O |
OH
Examples of Acid Catalysed Hydration:
Ques.

Ques.
Ques.

Ques.

Ques.
 Alkene ⟶ Alcohol
Hydroboration – Oxidation (HBO)
• AMK rule follow
• No carbocation ( No rearrangement)
• Syn – addition of H + from BH3 + OH (from H2 O2 /OH⊖ )
BH3 /THF
• 3 R − CH = CH2 R − CH − C H2
or B2 H6 | |
H BH2

R−CH2 −CH3
R − CH3 − CH2 3 B R − CH2 − CH2 2 − BH

3 H2 O2 /OH⊖ (oxidation)

3 R − CH2 − CH2 − OH + B OH 3
Examples of Hydroboration Oxidation:
Ques.

Ques.
Ques.

Ques.

Ques.
 Oxymercuration – Demercuration:- (OMDM)
OH add OH
(1) Hg OAC 2 /H2 O |
R − CH = CH2 R − C H − CH2
|
(2) NaBH4 H
H add
• MK rule follow
• Non classical cation is formed (no rearrangement )
• Anti addition reaction
 Hg OAC 2 /H2 O
Step (1) R − CH = CH2 R − CH − CH2
(Oxymercuration)

H g ⊕ (cyclic Mer curium ion)

|
oAC

⊕
O H2 OH
Step (2) R − CH − CH2 H2 O | −H ⊕ |
R − CH − C H2 R − C H − CH2
|
Hg−oAC |
Hg(oAC)

H g⊕
|
oAC
 OH OH O
| Na⊕ BH4⊖ | −
Step (1) R − CH − CH2 R − C − CH2 + Hg + + O − C − CH3 … … … … .
|
(demercuration) H

H
|
H−B−H
|
H
Examples of Oxymercuration – Demercuration:
Ques.

Ques.
Ques.

Ques.
Ques.

Ques.
Ques.

Ques.
Ques.

Ques.
Ques.

Ques.
 Alkyl halide ⟶ Alcohol
aq. KOH SN 2 R-OH
(i) R − X
Mosit Ag 2 O SN 2 (alcohol)
1°/ 2° Alkyl halide aq. NaOH
aq. NaHCO3
aq. Na2 CO3
aq. Ba OH 2

H2 O/R− OH
(ii) R − X R − OH
SN1 (PPS)
(alcohol)
2°/ 3° Alkyl halide
Examples of preparation of alcohol from alkyl halide:
Ques.

Ques.
Ques.

Ques.
 From aldehyde/Ketone:-
O
Reduction
R−C−H R − CH2 − OH (1°alcohol)
O
,, OH
R−C−H |
R − CH − R(2°alcohol)
H2 /Δ
(i) Catalytic hydrogenation
Ni/Pt/Pd

(ii) LiFilH4 and NaBH4

↓
H ⊖ H H ⊖ H
Al Li+ Na+ B
H H H H
❑ Catalytic hydrogenation.

O
|| 𝑯𝟐 /𝚫

C 𝑵𝒊/𝑷𝒕/𝑷𝒅 𝐑 − 𝐂𝐇𝟐 − 𝐎𝐇
▪ R H (𝟏° 𝐚𝐥𝐜𝐨𝐡𝐨𝐥)

O
|| ,,
▪ 𝐑−𝐂−𝐑
(𝟐° 𝐚𝐥𝐜𝐨𝐡𝐨𝐥)
Examples of preparation of alcohol by reduction:
Ques.
H2 / ∆
CH3 − CH = O
Pt / Pd / Ni

Ques.
O
|| H2 / ∆
CH2 = CH − CH2 − C − R
Pt / Pd / Ni
(ii) Reduction via 𝐋𝐢𝐀𝐥𝐇𝟒 and 𝐍𝐚𝐁𝐇𝟒

Strong R.A Mild R.A

NaBH4 is lens reactive compared to LiAlH4 because NaBH4 has more covalent
character than LiAlH4

𝐎
|| 𝟏 𝐋𝐢𝐀𝐥𝐇𝟒
𝐑−𝐂−𝐇 𝐑 − 𝐂𝐇𝟐 − 𝐎𝐇
𝟐 𝐇+ /𝐇𝟐 𝐎
Examples of preparation of alcohol by reduction via LiAlH4 and NaBH4:
Ques.
O
|| i LiAlH4
H−C−H
ii H+ / H2 O

Ques.
O
|| i LiAlH4
H−C−H
ii D+ / D2 O
Ques.

i LiAlH4
ii D+ / D2 O

Ques.

i NaBD4
ii H+
Ques.

i LiAlD4
ii H2 O

Ques.

i LiAlH4
ii D2 O
 (5) Carboxylic acid and derivative

(i) Reduction via 𝐋𝐢𝐀𝐥𝐇𝟒 and 𝐍𝐚𝐁𝐇𝟒

➢ 𝐋𝐢𝐀𝐥𝐇𝟒 reduce all the carboxylic acid and its derivative but 𝐍𝐚𝐁𝐇𝟒 only
reduce acid halide 𝐎
||
𝐑 − 𝐂 − 𝐂𝐥

(ii) Reduction via 𝐇𝟐 /𝐍𝐢/𝐏𝐭/𝐏𝐝.

𝐎
||
➢ 𝐇𝟐 /𝐍𝐢/𝐏𝐭/𝐏𝐝 reduce all the carboxylic acid derivative except. 𝐑 − 𝐂 − 𝐎𝐇
 Ques.
Ques.
O
O ||
|| i NaBH4
ሷ 2 / OR
LiAlH4 ሷ 2
R − C − OH / OR / NH
R − C − OH / Cl / NH ii H2 O / H+

Ques.

O
|| H2 / Pd / Pt / Ni
R − C − OH
Ques.
O
|| i NaBH4
R − C − Cl
ii H2 O / H+ Ques.
O
|| H2 / Pd / Pt / Ni
ሷ 2
R − C − Cl / OR / NH
Ques.
O
|| i LiAlH4
C−H
ii D2 O / D+

Ques.
O
|| i LiAlH4
CH3 − C − O − CH3
ii H+ / H2 O

Ques.

i LiAlH4
ii H+ / H2 O
Ques.
O
|| i LiAlH4
CH3 − C − OEt
ii D+ / D2 O

Ques.

i LiAlH4
ii H+ / H2 O
Ques.
O
|| LiAlH4
CH2 = CH − CH2 − C − CH2

Ques.
O
|| NaBH4
CH2 = CH − CH2 − C − CH2

Ques.
O
|| H2 / Pd, Pt, Ni
CH2 = CH − CH2 − C − CH2
Functional Group Products LiAlH4 NaBH4 H2/Ni, Pd, Pt
O
||
R−C−H

O
||
R1 − C − R 2

O
||
R − C − Cl

O
||
R − C − O − R′
Functional Group Products LiAlH4 NaBH4 H2/Ni, Pd, Pt

O
||
ሷ 2
R − C − NH

O
||
R − C − OH

R − CH = CH2
(6) From Grignard → alcohol

(i) Nucleophilic addition reaction.

(ii) Nucleophilic addition elimination.
(i) Nucleophilic addition reaction:

𝐎
|| 𝟏 𝐂𝐇𝟑 𝐌𝐠𝐂𝐥
𝐑−𝐂−𝐇
𝟐 𝐇 + /𝐇𝟐 𝐎
Nucleophilic Addition Reaction:
Ques.

Ques.
Ques.

Ques.
Nucleophilic Addition Elimination:
Ques.

Ques.
 𝑯𝟐 𝑶
(7) Ester alcohol (By hydrolysis).
Examples of preparation of alcohol from ester:
Ques.
O
|| H2 O
CH3 − C − OC2 H5

Ques.
O
|| H2 O
CH3 − C − O − Ph
Ques.

H2 O
(8) Primary amine → alcohol (using diazonium salt)
Examples of preparation of alcohol from primary amine:
Ques.
NaNO2 +HCl
ሷ 1
CH3 − CH2 − CH2 − NH

Ques.

NaNO2 +HCl
Alcohol, Phenol & Ether
❑ Chemical Reaction of Alcohol:- 𝐑−𝐎−𝐇

1. Reaction with metals.

2. Esterification reaction.
3. Reaction with aldehydes/ketone.
4. Reaction with Grignard.

❑ Reaction involving cleavage of Oxygen-Hydrogen bond

(1) Reaction with hydrogen halide.

(2) Reaction with 𝑷𝑪𝒍𝟓 and 𝑷𝑪𝒍𝟑 .
(3) Reaction with 𝑺𝑶𝑪𝒍𝟐 (Darzen reaction).
(4) Dehydration.
(5) Oxidation of alcohol
𝐇 + /𝐊𝐌𝐧𝐎𝟒

𝐇 + /𝐊 𝟐 𝐂𝐫𝟐 𝐎𝟕

𝐂𝐫𝐎𝟑

𝐏𝐂𝐂
Pyridium choro chromate
𝐂𝐮/𝟑𝟎𝟎°

𝐇𝐈𝐎𝟒
(a) Reaction involving cleavage of O-H bond:-
(1) Reaction with Metal:-

𝐑 − 𝐎 − 𝐇 + active Metal
(𝐍𝐚, 𝐊, 𝐀𝐥)

𝟐𝐑 − 𝐎 − 𝐇 + 𝟐𝐍𝐚 →

𝐂𝐇𝟑
|
𝐂𝐇𝟑 − 𝐂 − 𝐎𝐇 + 𝐀𝐥 →
|
𝐂𝐇𝟑
(3) Esterification Reaction:

Carboxylic acid
Alcohol 𝐂𝐨𝐧𝐜 𝐧 𝐇𝟐 𝐒𝐎𝟒
Acid chloride Ester
Acid anhydride 𝚫
Examples of Esterification Reaction:
Ques.

Ques.

Ques.
Reaction with aldehyde/ketone:
Ques.
O
||
R − C − H + 2R − OH ⟶

Ques.
O
||
R − C − R + 2ROH ⟶
Reaction with Grignard:
Ques.
CH3 − MgBr + CH3 − CH2 − CH2 − OH ⟶
❑ Chemical Reaction of Alcohol:- 𝐑−𝐎−𝐇

1. Reaction with metals.

2. Esterification reaction.
3. Reaction with aldehydes/ketone.
4. Reaction with Grignard.

❑ Reaction involving cleavage of Oxygen-Hydrogen bond

(1) Reaction with hydrogen halide.

(2) Reaction with 𝑷𝑪𝒍𝟓 and 𝑷𝑪𝒍𝟑 .
(3) Reaction with 𝑺𝑶𝑪𝒍𝟐 (Darzen reaction).
(4) Dehydration.
 Reaction involving cleavage of R−O bond
Reaction with Hydrogen halide:

Ques.
ZnCl2
1° alc. R − CH2 OH + Conc. HCl
∆

Ques.
ZnCl2
2° alc. R 2 CHOH + Conc. HCl
Ques.
ZnCl2
3° alc. R 3 COH + COnc. HCl
Reaction with PCl5 & PCl3, :
Ques.
R − O − H + PCl5 ⟶

Ques.
∆
R − O − H + PCl3
(3) Reaction with 𝑺𝑶𝑪𝒍𝟐 : − darzen reaction.

𝐑 − 𝐎𝐇 + 𝐒𝐎𝐂𝐥𝟐 → 𝐑 − 𝐂𝐥 + 𝐒𝐎𝟐 + 𝐒𝐎𝟐 ↑ +𝐇𝐂𝐥 ↑

𝐠𝐚𝐬𝐞𝐬

Ques.
darzen
CH3 − OH + SOCl2
reaction
 Dehydration

(4) Dehydration (Removal of 𝐇𝟐 𝐎)

𝐂𝐨𝐧𝐜.𝐧 𝐇𝟐 𝐒𝐎𝟒 𝐇𝟑 𝐏𝐎𝟒 𝐀𝐥𝟐 𝐎𝟑 𝐚𝐜𝐡𝐲.𝐙𝐧𝐂𝐥𝟐

𝚫 𝚫 𝚫 𝚫
Protonation of alcohol
H+ ⊕
CH3 − CH2 − CH2 − OH 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐎𝐇𝟐

Formation of carbocation (Rearrangement possible)

+ ⊕
CH3 − CH2 − CH2 − OH2 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 + 𝐇⊕

Alkene formation
+
CH3 − CH − CH3 𝐂𝐇𝟐 = 𝐂𝐇𝟐 + 𝐇⊕
Ques.

Ques.
Ques.
Ques.
100°C
C2 H5 OH + Conc. H2 SO4

Ques.
140°C
C2 H5 OH + Conc. H2 SO4

Ques.
170°C
C2 H5 OH + Conc. H2 SO4
Oxidation of Alcohol
Oxidation of Alcohol:
Ques.
OH
| H+ / KMnO4
R − CH − R′
H+ / K2 Cr2 O7

Ques.
OH
| 𝐂𝐫𝐎𝟑
R − CH − R′

Ques.
R′′
|
R − C − R′ ⟶
|
OH
 𝐇 +/𝐊𝐌𝐧𝐎
+ acid
𝐇 /𝐊 𝟐 𝐂𝐫𝟐 𝐎𝟏
𝐂𝐫𝐎𝟑 aldehyde
𝟏° 𝐚𝐥𝐜𝐨𝐡𝐨𝐥

𝐏𝐂𝐂
Aldehyde(good yield)

𝐇 + /𝐊𝐌𝐧𝐎𝟒 Ketone
𝐡𝐢𝐠𝐡 𝐭𝐞𝐦𝐩.
acid
𝟐° 𝐚𝐥𝐜𝐨𝐡𝐨𝐥
𝐂𝐫𝐎𝟑

𝟑° 𝐚𝐥𝐜𝐨𝐡𝐨𝐥 No. oxidation

❑ Oxidation with 𝐇𝐈𝐎𝟒 : 𝐕𝐢𝐜𝐢𝐧𝐚𝐥 𝐎𝐇 , 𝐂𝐢𝐜𝐢𝐧𝐚𝐥 𝐂 = 𝐎 , 𝐕𝐢𝐜𝐢𝐧𝐚𝐥 𝐂 = 𝐎 & 𝐎𝐇
Ques.
O OH O
|| | || HIO4
CH3 − C − CH − CH2 − C − H
Oxidation with Cu/300°C (Test 1°/2°/3° Alcohol):
Ques.
Cu / 300°C
CH3 − CH2 − OH

Ques.
OH
| Cu / 300°C
CH3 − CH − CH3
Ques.
CH3
| Cu / 300°C
CH3 − C − OH
|
CH3
 Test of Alcohol

(1) Lucas Test ⟶ Conc. HCl + ZnCl2

1° Alcohol ⟶

2° Alcohol ⟶

3° Alcohol ⟶
(2) Victor Mayer’s Test (Colour test of alcohol)

1° Alcohol ⟶
2° Alcohol ⟶
3° Alcohol ⟶
𝑷+𝑰𝟐 𝑨𝑮𝑵𝑶𝟐 𝑯𝑵𝑶𝟐
𝑹 − 𝑪𝑯𝟐 − 𝑶𝑯 𝑹𝑪𝑯𝟐 − 𝑰 𝑹 − 𝑪𝑯𝟐 𝑵𝑶𝟐 𝑹𝒆𝒅. 𝑪𝒐𝒍𝒐𝒓

𝑷+𝑰𝟐 𝑨𝑮𝑵𝑶𝟐 𝑯𝑵𝑶𝟐

𝑹𝟐 − 𝑪𝑯 − 𝑶𝑯 𝑹𝟐 𝑪𝑯𝑰 𝑹𝑪𝑯𝟐 𝑵𝑶𝟐 𝑩𝒍𝒖𝒆. 𝑪𝒐𝒍𝒂𝒓

𝑷+𝑰𝟐 𝑨𝑮𝑵𝑶𝟐 𝑯𝑵𝑶𝟐

𝑹𝟑 𝑪𝑶𝑯 𝑹𝟑 𝑪𝑰 𝑹𝟑 𝑪𝑵𝑶𝟐 𝑪𝒐𝒍𝒂𝒓𝒍𝒆𝒔𝒔
(3) Dichromate Test (Only distinguish 3°)

𝐇 + 𝐊 𝟐 𝐂𝐫𝟐 𝐎𝟕
1° Alcohol

𝐇 + 𝐊 𝟐 𝐂𝐫𝟐 𝐎𝟕
2° Alcohol

𝐇 + 𝐊 𝟐 𝐂𝐫𝟐 𝐎𝟕
3° Alcohol
 Phenol
OH

• Phenol also called carbolic acid/Benzenol/Hydroxybenzene.

• All phenolic compounds give characteristic colur with neutral 𝑭𝒆𝑪𝒍𝟑

𝑵𝒆𝒖𝒕𝒓𝒂𝒍
𝑷𝒉 − 𝑶𝑯 Violet colour
𝑭𝒆𝑪𝒍𝟑
𝑵𝒆𝒖𝒕𝒓𝒂𝒍
𝑹 − 𝑶𝑯 No colour
𝑭𝒆𝑪𝒍𝟑
 Method of Preparation
➢ Method of preparation:-
𝑶𝒙𝒊𝒅𝒂𝒕𝒊𝒐𝒏
1. Benzene
𝑽𝟐 𝑶𝟓 /𝟑𝟎𝟎℃
𝑵𝒂𝑶𝑯
2. Chlorobenzene (dow’s process)
𝟑𝟎𝟎℃ & 𝟑𝟎𝟎 𝒂𝒕𝒎
3. Benzene sulphonic acid.
4. Benzene diazonium salt.
5. From cummene
6. Salicylic acid (soda-lime decarboxy lation)
(1) Benzene
(2) Chloro Benzene
Ques.

Ques.
Ques.

Ques.
(3) Benzene Sulphonic Acid

SO3 H O− Na+
NaOH HCl
(4) Benzene diazonium salt
(5) From cummene

From cumene: (Industrial preparation of phenol)

oxidize dil
Cumene + air 𝑂2 cumene hydroperoxide Phenol+ acetone
acid
Ques.

Ques.
(6) Salicylic acid (Soda-lime decarboxylation)
 CHEMICAL REACTION:-
(2) Due to benzine Ring (Electrophilic aromatic substation): -
1. Nitration
2. Halogenation
3. Sulphonation
4. Riemer – Tieman Rx n
5. Reaction with zn – dist.
6. Oxidation
7. Friel craft Relation
Reaction with metal:
Ques.

Ques.
 Esterification
(A) Acetylation
Ques.

Ques.
(1) Nitration:
Reaction due to Benzene Ring (Electrophilic aromatic substitution Reaction)
➢ Phenol is O/P directing
OH
OH
Conc. HNO3 NO2 2,4,6 - trinitrophenol
NO2
(Picric acid) Pale yellow
NO2
(2) Halogenation:
Ques.
Since Phenol is activating in nature, so lewis acid is not req.
Ques.

Ques.
(3) Sulphonation:
Ques.
(4) Kolbe schmidt reaction:
Ques.
 (5) Reimer-tieman reaction:

𝒂𝒒.𝑵𝒂𝑶𝑯
Phenol + Chloroform aldehyde group at ortho position of phenol (Sali aldehyde)
Ques.

Ques.
Ques.
(6) Reaction with Zn-dust:
Ques.

Ques.

Ques.
(7) Oxidation of phenol:
Ques.
(8) Friedel craft reaction:
⟹ Friedel craft alkylation
Ques.
Ques.

Ques.
⟹ Friedel craft acylation
Ques.

Ques.