Monohydric Alcohols

029 TsCl/Py CH3 — CH2 — O — Ts

H2SO4, 140°C
CH3 — CH2 — O — CH2 — CH3 025
Ether formation

030 HX CH3 — CH2 — X

H2SO4, 180°C
CH2 == CH2 β–elimination 026

To avoid the formation of

peroxide, ether is always ke
pt in brown coloured
bottles CH3 — CH2 — OH
with small amount of Cu2O
and H2SO4 or FeSO4

HI or TsCl/Py
031 R—H
Na or NaH followed by LiAlH4
CH3 — CH2ONa 027
Salt formation

PCl5 or PCl3 CH3 — CH2 — Cl

032 or SOCl2
(CH3)2SO4/NaOH or CH3I
CH3 — CH2 — O — CH3 Methylation 028

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 Monohydric Alcohols R — CH2OH
(i) KMnO4/OH/Δ
(ii) KMnO4/H /Δ
RCOOH
MnO2 and aluminum tertiary
butoxide oxidise only alcoholic
(iii) K2Cr2O7/H /Δ groups and have no effect on
(iv) conc. HNO3/Δ other oxidizing groups.

CH3 — CH2 — Br PBr3 or P/Br2Δ 033

036 Mild oxidising agent CH3 — CHO

CH3 — CH2 — I PI3 or P/I2/Δ 034 CH3 — CH2 — OH

Strong oxidising agent,

OC2H5 037 CH3 — COOH
KMnO4/OH/Δ
R — CH == CH2/H2SO4 035
R — CH — CH3

Oxidation with O2/Pt: It oxidizes primary alcoholic groups

into
carboxylic groups and has no effect on secondary and tertiary hydr
oxyl
groups.
Oxidation of tosylate ester of alcohols with DMSO: In this
Jones reagent (solution of chromic acid and sulfuric acid in wate
r) is also used to oxideze 1° alcohols to acid and 2°
reaction alcohols to
primary and
(i)secondary
P/I2/Δ alcohols convert into carbonyl
(a) Formation compounds.
of red colour ketone. The oxidation of alcohol is indicated by a change in the
(ii) AgNO2 solution → 3° alcohol colour of the solution from orange to green.
Alcohol (b) Formation of blue colour
(iii) NaNO2/conc. H2SO4
solution → 2° alcohol
(iv) OH
(c) No colour → 3° alcohol

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 Monohydric Alcohols • Ketones undergo coupling reaction via reduction to give vic. Diols. Coupling takes
place with Mg/Hg.

• Aromatic aldehydes give above reaction with Na/C2H5OH

Cl
SOCl2
CH2 — CH2Cl
HCl Br
CH2OH — CH2 — Cl
60° PBr3
C CH2 — CH2Br
HCl
CH2Cl — CH2Cl
200°C
CH2OH — CH2OH
Pl3
[CH2I — CH2 — I] H3C == CH2 + I2
PCl5
CH2Cl — CH2Cl
HI/P HI
CH3 — CH2I Δ
CH3 — CH3

In case of oxidation of α− hydroxyl carbonyl compounds, carbonyl group always oxidised into carboxylic group.

O—H O—H CH == O — H CHO

O—H
C6H5 C6H5
OHOH O OHOH O
H2SO4 C6H5 — C — C — CH3 H2SO4 CH3 — C — C — CH3
C6H5 — C — C — CH3 CH3 — C — C — CH3

C6H5 CH3 C6H5 C6H5 C6H5 C6H5

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 Electrophilic Aromatic Substitution Reactions of Phenol

OH OH
OH OH
SO3H
NO2
20% HNO3 H2SO
25°C 038 043 4
100°
3 SOH
NO2 C
Major product

OH OH OH
OH
NO2 NO2 SO3H
Conc. HNO3 H2SO
H2SO4/Δ
039 042 4
25°C
NO As majo
2
r SO3H
Picric acid
product

OH OH OH
Br Br Br2/HOH or Br2/CCl4 or
Br
040 041 Br2/CS2
Br2/CH3COO
H
Br Br

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 Electrophilic Aromatic Substitution Reactions of Phenol

OH O
OH OH

(i) CHCl3/alc. KOH

CHO
HNO2 or
NaNO2 + conc. HCl 045 049
(ii) H2O/H
NO N — OH Reimer-Tiemann Reaction (Major product)
p-Nitrosophenol
CHO

OH OH OH OH
R
OH (i) RCN/HCl gas
C R
R—X Anhy. ZnCl2
044 048
Anhy. AlCl3Δ (ii) H2O/H (Major product)
Houben-Hoesch o-acylphenol C O
R Reaction
Very poor yield (≈ 10%) R

OH OH
OH
CHO
(i) (i) (CH2)6N4/KOH
046 047 CHO
Zn(CN)2 /HCl gas (ii) H2O/H
Major product (ii)HOGattermann2 Duff Reaction
salicylaldehyd CHO Aldehyde Syn.
e

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 Electrophilic Aromatic Substitution Reactions of Phenol

OH OH
OH
COOH
(i) CCl4/alc KOH/Δ Hg(OAc)2 HgAc
050 053 Re lux
(ii) H2O/H Mercuration
Major produc Reimer-Tiemann
COOH
t salicylic acid Reaction
OH

OH
(i) HO N == N — Ar
COOH
Kolbe CO2/NaOH (i) NaOH(pH 7.5)
120°C, 7 atm 051 052
Reaction (ii)Ar — N ≡≡ NCl p-Hydroxyazobenzene
(ii) H
Salicylic acid (Azo dye) red-orange coloured

OH

Salicylic acid derivates and drugs: Some of the COOH

+HO
most
common medications are the derivates of salicyl
OH O PCl5 –HOH
ic acid. Salicylic acid itself is used as
disinfectant in C — O — C6H5
some irst aid sprays and ointments
Phenyl Salicylate: (salol) (Salol)

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 Conc. H2SO4 (1 mole)
R — OH + R — O — SO3H Warm 054 Reaction of Ether
Conc. H2SO4 (1 mole)
R — O — SO3H + R — O — SO3H Warm 055

HOH/Δ/High pressure
R — OH + R — OH 056
H

HI (1 mole)
R — I + R — OH 057
Cold

3 mole HI/red P δ–
R—H+R—H Δ
058 R—O—R

2HI
R—I+R—I Cold
059
O
δ–
O R’ — C — Cl
δ+
060 Oxidation of ether can only be
R — Cl + R — O — C — R’ Anhy. ZnCl2 possible if any one of the alkyl
O O groups of ether has hydrogen on
R’ — C — O — C — R’ α−carbon
O O
061
R — O — C — R’ + R — O — C — R’ α−carbon having two halogens
converts into carboxylic group
and α−carbon having only one
PCl5/ hydrogen converts into keto group
R — Cl + RCl + POCl3 062
Δ

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