1

Alcohols


Alcohols

Bilal Hameed Alcohols

 strengths of the C–X bonds as exemplified by the reactions of halogenoalkanes with aqueous silver nitrates)

2
16 Hydroxy compounds
16.1 Alcohols
Learning outcomes
Candidates should be able to:
1 recall the reactions (reagents and conditions) by which alcohols can be produced:
(a) electrophilic addition of steam to an alkene, H2O(g) and H3PO4 catalyst
(b) reaction of alkenes with cold dilute acidified potassium manganate(VII) to form a diol
(c) substitution of a halogenoalkane using NaOH(aq) and heat
(d) reduction of an aldehyde or ketone using NaBH4 or LiAl H4
(e) reduction of a carboxylic acid using LiAl H4
(f) hydrolysis of an ester using dilute acid or dilute alkali and heat
2 describe:
(a) the reaction with oxygen (combustion)
(b) substitution to halogenoalkanes, e.g. by reaction with HX or KBr with H2SO4 or H3PO4; or with PCl 3 and
heat; or with PCl 5; or with SOCl 2
(c) the reaction with Na(s)
(d) oxidation with acidified K2Cr2O7 or acidified KMnO4 to:
(i) carbonyl compounds by distillation
(ii) carboxylic acids by refluxing
(primary alcohols give aldehydes which can be further oxidised to carboxylic acids, secondary alcohols
give ketones, tertiary alcohols cannot be oxidised)
(e) dehydration to an alkene, by using a heated catalyst, e.g. Al 2O3 or a concentrated acid
(f) formation of esters by reaction with carboxylic acids and concentrated H2SO4 or H3PO4 as catalyst as
exemplified by ethanol
3 (a) classify alcohols as primary, secondary and tertiary alcohols, to include examples with more than one
alcohol group
(b) state characteristic distinguishing reactions, e.g. mild oxidation with acidified K2Cr2O7, colour change
from orange to green
4 deduce the presence of a CH3CH(OH)– group in an alcohol, CH3CH(OH)–R, from its reaction with alkaline
I2(aq) to form a yellow precipitate of tri-iodomethane and an ion, RCO2–
5 explain the acidity of alcohols compared with water

Back to contents page www.cambridgeinternational.org/alevel 31

Alcohols Bilal Hameed

 93 3

1 Alcohols
The simplest alcohols form a homologous series of general formula
CnH2n+1OH provided there are no rings.

Named as substituted alkanes by removing the final -e and adding -ol

For isomers the position of the OH is given by a number propan-1-ol and

propan-2-ol

ten
*PH¥**±¥t¥* . *±¥t¥*
'

it OH OH H

methanol ethanol

2 Alcohols
The —OH group is called the hydroxyl group. When drawing alcohols always make
sure the bond goes to the O.

The functional ten

*PH¥**±¥t¥*
.group, however, is referred to as primary/secondary/tertiary alcohol as *±¥t¥*
'

chemical behavior of alcohols, especially withit oxidation,

OH often depends
OH H on the structure
of the alcohol.

methanol ethanol

Alcohols may be described as primary, secondary or tertiary, depending on the number

of H atoms attached to the carbon with the –OH group on it.
ps0pan-tolpopantHzCHz-CHz-CHz-CHz-OACH5CHzgH-CH3.bntan-tohaprimamaKohdoHCH5c-CHzbn1anto1.asecondaryalahdoH2-methylpropan-2-ol.atertiaryaboud@0oceHsVYagatcHsceoe0ooCHzcHIhAstHTYnioo.S-ooq.m

ps0pan-tolpopantHzCHz-CHz-CHz-CHz-OACH5CHzgH-CH3.bntan-tohaprimamaKohdoHCH5c-CHzbn1anto1.asecondaryalahdoH2-methylpropan-2-ol.atertiaryaboud@0oceHsVYagatcHsceoe0ooCHzcHIhAstHTYnioo.S-ooq.m

3 Primary Alcohols
Ethanol is a primary alcohol, as it has two hydrogens attached to the C with the
–OH attached.

A primary alcohol thus contains the –CH2OH group.

A In }
\

,%fI
A H

:#
A Cttzutz
μ H
a
C- C-HμH
A
zaatomsatlaohed
.

Hitt
0 -
C- A
Cattachedtoott
I I

μ
Cattachedtoott \
A Cttzutz
A μ

Zcatoms attached

A
BilalBilal
HameedHameed Marginalizer H
Alcohols
I

it
 4 94

4 Primary Alcohols
Another way of looking at this is that the C with the –OH attached has one other C
attached to it.

One C attached = primary.

A In }
Catomaltached

,%fI
H

:#
H
a
C- C-HμH
A
zaatomsatlaohed
.

0
Hitt
-
C- A
Cattachedtoott
I I

A In
,%fI
H

:#
H
a
C- C
A
zaatomsatlaohed
.

Hitt

¥q€t
C-
bit
E- C-C-
0 -
C- A

atoms attached Cattachedtoott

Cattachedtoott
5 Secondary Alcohols

c-
A
I H
Propan-2-ol is a secondary alcohol, as it has one H atom attached to the C
with the –OH attached.
it A secondary alcohol contains the –CHOH group.
I

CASH
H I I
H A

"

¥q€t
}C-
bit
E- C-C-
-

ttihtirh Zcatoms attached

c-
t A
, ryatomaitached I H

it

A In
Catomaltached

,%fI
HH

:#
H I

CASH
I I
H
a
C-HμH
-

C-
A H A

"
zaatomsatlaohed
-

ttihtirh
0
Hitt-
C- A cattachedtout
Cattachedtoott ryatomaitached
I \ ,
I
t

μ
ttachedtoott
crzoihtt crzoiilitt
primary > aldehyde > carboxylic
alcohol heat heat acid

6 Tertiary Alcohols
crzoihtt crzoiilitt
> aldehyde primary > carboxylic
2-methylpropan-2-ol is a tertiary alcohol, as there
alcoholare noheat
H atoms (or three C heat acid

¥q€t
C-
bit
E- C-C-
0

*Pjf
attached atoms) attached to the C with the –OH attached.
Zcatoms

.tt#E*HttitceH*PHEat
c-
A
heat heat H
I
0

ethanol
H -
H
ethanol
*Pjf
.tt#E*HttitceH*PHEa
ethanoicacid

CASH
H
I I
it
I
A
heat heat

"
-

ttihtirh ethanol ethanol ethanoica

attachedtout \ , ryatomaitached
t

CHZCHZOH t[O] CHZCHO +Hz0

CHZCHO t[] CHzCOzH CHZCHZOH t[O] CHZCHO +Hz0

CHZCHO t[] CHzCOzH

crzoihtt crzoiilitt
primary > aldehyde > carboxylic
alcohol heat heat acid
Alcohols Marginalizer BilalBilal Hameed
Hameed
11
Craqtlttt 11
11
Craqtlttt 11
-

A -> -> c
-
-

A -> -> c
heat / / -
 Figure 16.2 Intermolecular hydrogen CH2 CH3
bonding in ethanol δ+
H O δ–

CH2 O δ– δ+H Oδ–

95 5 CH3 Hδ+ CH2 CH3

Table 16.1 and Figure 16.3 show this large difference. A

series, the boiling points increase as the number of carb
owing to increased van der Waals’ attractions between t
enhancement of boiling point due to hydrogen bonding
7 Properties 16_02 Cam/Chem AS&A2
chains become more alkane-like.
Barking Dog Art
Table 16.1 Boiling points of some alcohols
Alcohols are useful solvents and are key intermediates in the production of
and alkanes
Number of
electrons in
Alkane Al
Formula Boiling Formula
esters, which are important solvents for the paints and plastics industries. the molecule point/∞C
18 C2H6 −88 CH3OH
The polar —OH group readily forms hydrogen bonds to similar groups in other 26 C3H8 −42 C2H5OH

molecules. 34 C4H10 0 C3H7OH

42 C5H12 36 C4H9OH

This accounts for the following major differences between the alcohols and the 50 C6H14 69 C5H11OH
58 C7H16 98 C6H13OH
corresponding alkanes.
Figure 16.3 Boiling points of some alcohols
and alkanes

200

150

alcohols
100

boiling point/°C
8 Properties
50

Alcohols have higher boiling points than other organic molecules with similar 0
15 20 25 30 35 40
relative molecular masses. Methanol, with the lowest molar mass, is a liquid at number of electrons
ANIC CHEMISTRY room temperature.
–50

This is because of hydrogen bonding along with van der Waals’ forces between –100
The boiling points of the alcohols are all much higher than the corresponding
alcohol molecules.
(isoelectronic) Thisowing
alkanes, also explains why smallerhydrogen
to strong intermolecular alcoholbonding
molecules
(see mix and
The electron pairs around the oxygen atom in alcohols
to those around the oxygen atom in the water molecule
dissolve
Figureso well in water.
16.2).
16_03
of Cam/Chem
electrons (see AS&A2
Figure 16.4).
e 16.2 Intermolecular hydrogen CH2 CH3
ng in ethanol δ+ Barking Dog Art
H O δ– O
16.2 Isomerism and nomen
CH2 O δ– δ+H Oδ–
R 105° H As was mentioned in section 12.5, the alcohols are nam
CH3 Hδ+ CH2 CH3 the alkane stem of the compound. The longest carbon c
The oxygen atom in an alcohol has two
Intermolecular hydrogen bonding in ethanol Figure 16.4 The oxygen atom in an alcohol group is chosen as the stem. A numeral precedes the ‘-o
Table 16.1 and Figure 16.3 show this large difference. Ashas twolone
is usual pairs
in pairs
lone of of
homologous electrons
electrons. The boiling point of straight-cha
the ¬OH group along the chain.
16_04 Cam/Chem AS&A2
series, the boiling points increase as the number of carbon atoms increases,
282
owing to increased van der Waals’ attractions between the longer alkylDog
Barking chains.
Art The
(–CH2–) group is added, because th
enhancement of boiling point due to hydrogen bonding also decreases, as the longer
16_02 Cam/Chem AS&A2 between molecules increases as the
chains become more alkane-like.
Barking Dog Art increases. A similar trend is seen in t
9 Boiling PointsAlkane
181333_16_AS_Chem_BP_281-293.indd 282
16.1 Boiling points of some alcohols
kanes
Number of
electrons in
Alcohol Enhancement
of boiling
series.
Boiling Formula FormulaPoints/
Boiling Boiling
oC
the molecule
The forces between molecules
point/∞C point/∞C
point/∞C Figure 10.5 compares the boiling
must be broken for2 the
18 6
liquid to boil.
CH −88 CH3OH 65 153 group on the first carbon atom) wi
26 C3H8 −42 C2H5OH 78 120
34 CH 0 C3H7OH 97 97
be seen that both series show the sa
In alcohols, hydrogen
4 10
bonding is the increases as the number of C atoms
42 C5H12 36 C4H9OH 118 82
strongest intermolecular force,
50 C6H14 69 C5H11OH 138 69 C atom (Mr 32.05) has a higher boi
therefore,
58 more energy
C7H16 is needed
98 to C6H13OH 157 59
C atoms (Mr 72.17). It is important
e 16.3 Boiling points of some alcohols break the hydrogen bonds.
kanes the relative molecular mass (and he
And so200
the boiling points of alcohols may be made within a particular ho
is higher. homologous series. The boiling poi
150 due to the presence of hydrogen bo
alcohols
100
boiling point/°C

Table 10.2 shows various functiona

50 alkanes
encounter during the course. The o
0
have been highlighted.
15 20 25 30 35 40 45 50 55 60 ‘R’ may be used to stand for an alk
number of electrons
BilalBilal
HameedHameed
–50 acid may be represented
Marginalizer as ‘RCOOH
Alcohols

–100
 6 96

nd
n bo
10 Solubility

ge
dro
hy
The lower members of the series are very soluble in
water because of the hydrogen bonding.

si
E+j÷HL ⇐
s+
For example, ethanol is soluble in water in all

CH
÷
°j÷

\gH
St

si St
proportions, and this is because the –OH group

EL

°s÷
jH2

/H
s+H
÷
CHZ
allows it to hydrogen bond to water.
o/Hs+
bond

°j÷
St
hydrogen

=H
jH2\=H\gH⇐

...
EL

\o

\o
s+H
However, solubility decreases as the length of the

=H/H
CHZ

o/Hs+

St
s+EL
... bond

°÷
hydrogen
jH2\=H\gH⇐

jH2
hydrocarbon chain increases so that pentan-1-ol

s
\gH ...
Z
j÷ CH
...
and hexan-1-ol are only sparingly soluble in water.
CH

H
YH

s⇐+
Z

s
H2
H

,
,tH

hy
tH

dro
Ctt
H2
%o

ge

,
-

n
#

bo
sQOf+FE -

CH

nd

Y
Ctt
11 Combustion Of Alcohols 3
i CH

Hs+
YHHOEof
#
,tt%QF_
hy

H2 -

CH3

Ctt
Z

In a plentiful supply of oxygen, alcohols burn to produce carbon dioxide and

dro

Z
CH
_
hydrogen bond
Htv

Hs+
-

ge

YHHOE
H2 CH3
water:
n
Hz

of
#
,
bo

,tt%QF_
nd

hydrogen bond
C2H5OH + 3O2 ⟶ ,
2CO2
CHZ + -
3H2O CHZ -

2 C3H7OH +CHZ 9O2 ⟶ 6CO2 + CHZ

8H2O -
EY
CH
'

Z
CH#

CH
Z
a
z-§

Htv EY
Hz CHZ CHZ

H a
Htv EY a
tIs

Hz CHZ CHZ
'

H
12 Reaction With Sodium
OH
'

'

Reagent Sodium metal, Na

CH

Condition room temperature

zC§-

CHSCHZOH Na -7 CHZCHZO Nat kHz

-

+ +
5H

WIPE . *P¥Fonat
z +

μ
§tHz CHzCHz-§tIs C
CH

Alcohols are organic chemistry’s equivalent of water; water reacts with sodium
I

g- #
IZTOHTAQ ) OH
'

CHZCHZ
,

CHZCHZ CHZ
-

to produce hydrogen and so do alcohols. The reaction is slower with alcohols.

-

μ
CHZCHZ -

g- CHZ
H
IZTOHTAQ )
§tHz CHzCHz-§tIs
# CHzCH
§-5 CHZCHZ -
OH
'

tit
A H H H

itd- NW

Hk
'
H - -
it -

Hk
'
it
at

CHZCHZCHCOH)

Alcohols Marginalizer BilalBilal Hameed

Hameed

it
t H

CHZCHCOH ) CHAO
'±E
- -

'
 WIPE . *P¥Fonat
97 7

tit
A H H H

itd- WithitSodium - NW

Hk
'

13 Reaction - -

Hk
'
it
atH

tit
A H H

itd-

at
NW

Hk
'

CHZCHZCHCOH) - -
it -

Hk
'
it
at

at
CHZCHZCHCOH)

it it
t H

it .
'±E .
'
-
,

it
TH TH t

it
H
it
'±E
-

'
it .
.
-
,

TH TH
CCHDZCHCHGH)CHCoH)CHz
it -

CCHDZCHCHGH)CHCoH)CHz

14 Alcohols To Alkenes
When an alcohol is heated with excess concentrated sulphuric acid at around
200 oC an alkene is formed. (Refer to the notes on Alkenes).
Dehydration of the alcohol can also be carried out by passing the alcohol
vapour overEsters
alumina
either an acid or at 350 oC. under reflux with
can be hydrolysed by heating
a base.
ceramic wool
soaked in ethanol
Refluxing with an acid simply reverses the preparation
Reagent ofConc
the ester H 2SO
from 4
an alcohol and a carboxylic acid. The acid
pumice

catalyses the reaction. The reaction is reversible and forms ethene gas collected
Condition an200 o C mixture. In acid hydrolysis, there are always
equilibrium over water
both reactants and products present after the reaction. The
Alternativelyequation
Alumina at 350
for the acid oCof ethyl ethanoate is:
hydrolysis
heat
Type Elimination
¥
¥
O H+(aq) O
H3C C + H2O H3C C + CH3CH2OH
+ Hzo
¥
¥
O CH2CH3 c- O H
,
c-
μ ,
+ Hzo
μ
However, when an ester is refluxed OH
with an alkali (a
+
soluble base), such
OH as aqueous sodium hydroxide, it is
+ Figure 16.7 The dehydration of ethanol to give ethene.
fully hydrolysed. Unlike acid hydrolysis, this is not a

¥
¥
reversible reaction. An alcohol and the sodium salt of the
acid are formed. The equation forc-the base hydrolysis of +
porous pot or pumice also catalyse theHzo
reaction.
ethyl ethanoate is: ,
μ OH
For example:

O + O
Al2O3 catalyst
C2H5OH → CH2 CH2 + H2O
A A H H H ethanol ethene water
A A H3C H C + NaOH H3C C + CH3CH2OH

15itctt
d- cttd-#
' CH2CH3 – +
' O sodium O Na Figure 16.7 shows how the ethene gas formed can
it
Alcohols to #Alkenes ethanoate be collected.
.
.

Ak ath
.

'
.

'

Ak ath
' '

Check-up Check-up
A A
CHZCHZCHCOH H H

ctt
d-
¥s#at
'
5 a Name the ester formed in each of the 6 Concentrated sulfuric acid or phosphoric
CHZCHZCHCOH

¥s#at
# reactions:
following acid can also be used to catalyse the
it
.
.

dehydration of an alcohol. The alcohol

Ak ath
' ' i butan-1-ol + ethanoic acid

)CH:
ii ethanol + hexanoic acid and concentrated acid are heated to about
iii pentan-1-ol and methanoic acid. 170 °C. The concentrated acid does not
change chemically during the reaction.

)CH:
b Write the structural formula of each ester
a Write an equation showing the
CHZCHZCHCOH formed in part a.

¥s#at
dehydration of ethanol using concentrated
+ A
Magana heat sulfuric acid.

)CHCoH)CH:
.it#3E.i.i-H
THH
- b If propan-1-ol was used instead of ethanol,
+, 5 Dehydration name the organic product formed.

)CH:
Magana heat
TH + A
Alcohols can also undergo elimination reactions in

)CHCoH)CH:
.it#3E.i.i-H
THH
-

which water is lost and alkenes are formed. As the small

-
+, molecule removed from the alcohol molecule is H2O, this 6 Oxidation
( HDZCHCHGH
C reaction is also known as dehydration. On page 238 we saw how alcohols can be classified
TH catalyst
as primary, secondary or tertiary. For many reactions
alcohol → alkene + water
-

+ A
Magana heat the class of alcohol makes no difference to the type of

)CHCoH)CH:
.it#3E.i.i-H
The reaction takes place when alcohol vapour is passed products formed. In organic chemistry, we can usually

¥ine#
THH
-
+, ( HDZCHCHGH
C over a hot catalyst of aluminium oxide powder. Pieces of generalise for the whole homologous series. However,

-
242 TH 16 Alcohols and esters

( HDZCHCHGH
C

.it#3E.d.cl,+Na0HiIo
ted - c-

Br
+ Hbr

.it#3E.d.cl,+Na0HiIo
ted
BilalBilal
HameedHameed Hbr Marginalizer Alcohols
+

CHZCHZCHBRCHZ
- c-

Br
 8 98

16 Alcohols To Halogenoalkanes
Reagent PCl5, (PCl3 or SOCl2)
Condition room temperature (heat for PCl3 and SOCl2)
Type nucleophilic substitution

I
It It It It

C- C- at -> At
-

C- a
H H H

The reaction releases white fumes of HCl with PCl5

Note: this is another test for the “OH” group in alcohols and carboxylic acids

Colt
It It Conca HI H It Conc .HB It It

Arndt
I I I
And Brz
1
1 I
reap reap
C- C-
OR OR
the
-

I = At -

- Ht
-

Br
1 1 hehtanderretwk 1
1
hehtanderrettux 1 1

H H 17 Alcohols To Halogenoalkanes
A It H H

Reagent conc. HBr or conc. HI

Condition heat under reflux

I
Type nucleophilic
It It
substitution It It

Alternatively Red C- C- C- a

.tt#et+i+o
Phosphorous
at
and Br2 or Red Phosphorous
-> At
and I2 can
-

CHZCOZH + CHSCHZOH T H CHZCECHZCH

H
t HZO
also be used.
H }

Conc H2SO4 and NaBr can also be used to produce conc HBr.

* 'PHE* rotted 't = its,F¥ 'T

Colt
It It Conca HI H It Conc .HB It It

Arndt H
I I I
And Brz
1
1 I
reap reap
C- C-
OR OR
the
-

I = At -

- Ht
-

Br
'd ethanol
hehtanderretwk
ethanoicaa ethydetnanoate
hehtanderrettux
1 1 1
1 1 1

H H A It H H

I
It It It It

C- C- at -> At
-

C- a

.tt#et+i+o
H H H

t
T

Hal
Codtk
CHZCOZH CHSCHZOH CHZCECHZCH }
HzS04 HZO
(
+ t
cone
+
.

18 Alcohol
'PHE* Torotted
Esters its,F¥ 'T

ZCHSCHZOH
* 't =
0 0
ethandiocacid
c- OH
H

toe
When an alcohol is heated with a carboxylic acid in the presence of a small
#
Colt
It .HzS04 It ethanoicaa 'd Conca HI ethanol HconeIt ethydetnanoateConc .HB It It

Arndt
+ H H
HO
amount
C- of
I concentrated= I sulfuric acidAtas a catalyst, an ester is -formed.
c-
-
I I I
And Brz
1
I
-
- 1
reap reap
C-
OR OR
the I Ht Br
- -
-

hehtanderretwk hehtanderrettux
Reagent carboxylic acid andA conc.
It H
sulfuric acid, H2SO4
1 1 1
1 1 1

H H It H H
ethanol
60°C / heat t

Hal
Condition
( Codtk
+
HzS04 cone .

Type esterification / condensation / nucleophilic

ethandiocacid
c- OH ZCHSCHZOH
toe
0

#
0
substitution .HzS04 cone

ZH
n .tt#et+i+o
+ H H
HO c-
H
-

0 A T
-
-

H CHZCOZH + ICHSCHZOH CHZCECHZCH } t HZO

c- OH
I

out #
1 11 1
It1 H
cone HzS04
c-
.

-0
+ H
ethanol -
H
its,F¥ 'T
-
-

t * 'PHE* rotted H H
't =

ZH
n out
H 0 H A
'd did H
ethanoicaa ethane -1,2
c- #
-

1 11 1 1 cone HzS04
ethanol
c-
.

'd ethydetnanoate

-0
-
ethanoicaa OH + H -
-
H

t H H

ethanoicaa 'd ethane -1,2 -

did

Hal
( Codtk
+
cone . HzS04

ZCHSCHZOH
HO How
±
0 0
ethandiocacid
A c-

How
±
A
toe A- c- #
HO
cone .HzS04

c-
OH H

Hilo
HO c- + H -

c- OH c- -7Hilo
-

A- c-
-

OH it

c-
Alcohols c- BilalBilal
OHHameed
1

c-
I
it
Marginalizer H OH
I
A- A-
-7 -7 It H -7 Hameed
-
-

+ ethanol H H

gthanoica
+ ethanol H
ethanol H

ethanol ethanol
 importance of condensation

II
conc. H2SO4 It It It It
ethanol + ethanoic acid ethyl ethanoate
It It + water reactions
It It
C- a
heat
C- C- atCHSCHZOH

.tt#et+i+o
T -> CHZCECHZCH } Att
-

CHZCOZH HZO
C- C- at C- a
+

-> At
-

H 99its 9 H H

rotted ,F¥ 'T

H
H H
* 'PHE* 't =
The alcohol and the carboxylic acid have been joined together and H

ethanoicaa 'd ethanol water has beenethydetnanoate

eliminated (one H atom from the alcohol and –OH from Examiner’s tip
the carboxylic acid molecule). The product formed wh

I
It any alcohol and any carb
19 Alcohol ToIt Esters
It It

Colt
acid come together can
C-HIC-HI at tH C- .HB

Hal
It It ( Codtk cone HzS04
->It At a It It

Colt
Conca Conc

Arndt
+
.
-

I It It H1 It .HB
Conc I ItI It worked out simply by p
the The C- alcohol and
OR the carboxylic acid have been joined together and water has
Conca

Arndt
I
And Brz
1
reap reap
C- Br
ZCHSCHZOH
OR
I -

I =reap At
H joined together and
1 I -
H ORH reap And Brz
-
1
Ht
-
I I
the alcohol and carboxy
C- C-
OR
The alcohol and thethe carboxylic acid have
I ethandiocacid been
= At
0 0

been eliminated c-(one H atom from the alcohol

hehtanderretwk
# Itfromand –OH from the carboxylic
- Ht Br
from thetoe
hehtanderrettux
- -

1 1
-

.HzS04
together, so that the two
1
1
cone 1 1

water has been eliminated

H H (one H atom
1 hehtanderretwk
OH
alcohol and –OH
1 A Examiner’s
HO tip
hehtanderrettux
-
c- + H -
- H 1
1 H 1
H 1

acid Hmolecule). groups are next to each

I
A It
I
H The product formed when H H
the carboxylic acid molecule). It H

ethanol
any alcohol and any carboxylic removing H from the O
acid come together can be the alcohol and OH from
carboxylic acid and join

ZHn out
0 H A worked out simply by putting

Colt
H

It It
1
c- OH
11
HI
1 1 cone
#
HzS04
H It Conc .HB
the alcohol and carboxylic acid It It O of the alcohol to the
c- Conca

Arndt
.tt#et+i+o
.

-0
+ H -
-
H
T
-

I I
CHSCHZOH CHZCECHZCH thatt HZO of the carboxylic acid.

.tt#et+i+o
CHZCOZH I
Brz
1

} soAnd
t I
reap +
1
reap
together, the two O–HHt
C- C-
t OR OR
CHZCOZH= T
H H
the
-

I + CHSCHZOHAt -

CHZCECHZCH- } HZO
-

Br
ethanoicaa 'd ethane -1,2 did
hehtanderretwk groups are next to each other,
-

1
hehtanderrettux 1
1
1 1 1

A It
itsits
H H removing H from the OH of H H

* 'PHE*
* 'PHE*
rotted
rotted
't
't
=
=
,F¥ the alcohol and OH from the
,F¥carboxylic
'T
'T
acid and joining the
H

How
±
O of the alcohol to the C=O

HO
A H
ethanoicaa 'd ethanol
ethydetnanoate

C-}
c- Hilo
of the carboxylic acid.

A In
A- c-'d
OH it
c- Catomaltached

,%fI
1

c-
ethanolA- H H
OH

:#
ethanoicaa -7 -7 H
ethydetnanoate
-

a A

.tt#et+i+o
C- zaatomsatlaohed H T
Hμ
.

CHZCECHZCH }
+
CHZCOZH + CHSCHZOH H
H t HZO
Hitt
gthanoica
0 - ethanol
C- A ethanol I I
Cattachedtoott
μ
Cattachedtoott

t its,F¥ 'T

Hal
( Codtk HzS04

torotted
cone
+
.

Halc-
* 'PHE*
20 ( Codtk
Alcohol Esters 't +
cone HzS04
= .

ZCHSCHZOH
ZCHSCHZOH
H
0 0
ethandiocacid
c- OH
toe
0 'd ethanol
ethydetnanoate
#
ethanoicaa
0 .HzS04
ethandiocacid
cone

c-
toe #
H

¥q€t
C-
bit
E-
HO -
c- + H -
-

cone .HzS04
attached
OH HOZcatoms
c- - + H -
I I - H
It H
I I
A
It
ethanol H H
I
ethanol

Hal
C-
C-
( Codtk+
cone . HzS04 it

}
I

In
CASH
I I
H H
Catomaltached

,%fI
A
-

:#
H A H
a A
"
-

ZH
ZCHSCHZOH
n C-HμH
C-
H ttihtirh
0
.

zaatomsatlaohed
A H

ZH
n
c-
out #
H1
0 H11 00
\ ryatomaitached A HzS04 t

c- Hitt
ethandiocacid
cone
cattachedtout
c-
c-
1 1 .

-0 toe
out
0 A

##
C- H
OH , cone HzS04
cone .HzS04
-

1 11 + H - 1 1
-

I I
Cattachedtoott
c-
- .

-0
HO OHOH c- + + HH - H -
H μ
Cattachedtoott
- -
- -

t H I H I

t 'd It H H H
did
ethanoicaa ethane -1,2 -

ethanoicaa 'd ethanol

ethane -1,2 -
did

crzoihtt crzoiilitt
primary > aldehyde > carboxylic
alcohol heat acid

ZH
heat

n
0 H A

¥q€t
C-
bit
E-
H

c- OH attached
out #
1
Zcatoms
11 1 1 cone HzS04
c-A
.

-0
H

How±± CASH
+ H -

HO
-

c-
-

HO How
H
c- c-
A H H 0

Hilo
t

*Pjf
I
OH 'dit
c-
1

21A-ethanoicaa
Oxidation
c-
H OH
c-
-7 -7
Hilo
didA-

.tt#E*HttitceH*PHEat
-1,2
OH it
c-
-

ethane
A- c-

C-
C-
1

c-
-

H it OH
A- heat
-7 heat -7 -

+ H I I I
H H H
Primary and +secondary alcohols may be
H oxidised using
H an oxidising Hagent,
-

gthanoica
A

"
-

ethanol ethanol
ttihtirh
gthanoica
ethanol ethanol ethanoicacid
ethanol
such as: ethanol
cattachedtout \ ryatomaitached
t

(K Cr O /H+)
,
acidified potassium dichromate(VI) 2 2 7

How
±
acidified potassiumt[O]
manganate(VII) (KMnO4/H+).

HO
A
CHZCHZOH CHZCHO +Hz0

Primary c-
alcohols
OH it are
t[] oxidised
CHzCOzH first A-
of all to anHaldehyde (partial oxidation), and
c- Hilo c-
1

A- CHZCHO
c- further to a carboxylic acid (complete
OH -7 -7 -

then the aldehyde is oxidised oxidation). + H H

crzoihtt crzoiilitt

gthanoica
ethanol primary > ethanol
aldehyde > carboxylic
alcohol heat heat acid

Otirzoitlllt Craqtlttt
11 11

-> ->
hμ
-

A c

c-
heat heat / -
| o -
A
0

*Pjf
H

.tt#E*HttitceH*PHEat heat heat

ethanol ethanol ethanoicacid

*tEtI±I
.int#.tEtIte**e*ittEtIttEo heat heat
.

zmemylpropom -1-01 zmemylpbpanal Zmethylpbpanoicacid

BilalBilal
HameedHameedCHZCHZOH t[O] CHZCHO +Hz0 Marginalizer Alcohols

CHZCHO t[] CHzCOzH

 H -
I

¥q€t
C-C-
bit
E-
¥q€t
bit
E-
¥q€t
C-
bit
E-
H
H
-

ttihtirh
c- c- CASH
c- CASH
H

C-
C-
C-
C-"
C-
C-
" H
it
I
it
I I H
A
-
I I I
A

¥q€t
C-
bit
E- C-
-

ttihtirh I

CASH
I I
attached
H
H Zcatoms
\ ryatomaitached t
-

cattachedtout H A
\
"
t
-

c- CASH
,
cattachedtout
ttihtirh
A
, ryatomaitached
10 H
I
100
cattachedtout \ ryatomaitached
t

C-
, it
I I I
H -
H
H A

"
-

ttihtirh
crzoihtt crzoiilitt
\ ryatomaitached t

22 Oxidation
cattachedtout
Ofcrzoihtt
primary Primary
>
alcohol Alcohols
primary > crzoiilitt
aldehyde
,
>
aldehyde >
carboxylic heat heat
carboxylic
acid
alcohol heat heat acid
crzoihtt crzoiilitt
Primary alcohols are oxidised
primary >
to aldehydes,
aldehyde which,
> incarboxylic
turn, are even more easily
alcohol heat acid
oxidised to carboxylic acids. For example:
heat

*Pjf
0

*Pjf
crzoihtt crzoiilitt

.tt#E*HttitceH*PHEat
primary carboxylic

.tt#E*HttitceH*PHEat
alcohol
> aldehyde >
heat heat heat acid heat
heat heat
0

*Pjf
.tt#E*HttitceH*PHEat
ethanol
ethanol
heat
ethanol
0
ethanol
heat
ethanoicacid
ethanoicacid

*Pjf
.tt#E*HttitceH*PHEat
ethanol
CHZCHZOH
CHZCHZOH
heat
t[O]
t[O]
CHZCHO
CHZCHO
+Hz0
heat
ethanol
+Hz0
ethanoicacid

CHZCHO
ethanol t[]CHZCHO t[]
CHzCOzH CHzCOzH
ethanol ethanoicacid

CHZCHZOH t[O] CHZCHO +Hz0

CHZCHO t[] t[O]

CHZCHZOH
CHzCOzH
CHZCHO +Hz0

Otirzoitlllt
Otirzoitlllt
CHZCHO t[] CHzCOzH 11
Craqtlttt 11

->Craqtlttt
11 11
->
hμ
A c
->
-

->
hμ
A c

23 Oxidation ofc-PrimaryHc-
heat heat -
-

/
heat heat / - A
Alcohols
| o -

| o -
A

Otirzoitlllt
H

11
Craqtlttt 11

Otirzoitlllt
-> ->
hμ
-

A c

c-
heat heat / -
| 11
Craqtlttt 11 o -
A
-> ->
hμ
A c
H
-

c-
heat heat / -

*tEtI±I
| o A

*tEtI±I .int#.tEtIte**e*ittEtIttEo
-

.int#.tEtIte**e*ittEtIttEo
H .
.
heat heat heat heat

zmemylpropom -1-01
zmemylpropom -1-01 zmemylpbpanalzmemylpbpanal Zmethylpbpanoicacid
Zmethylpbpanoicacid

*tEtI±I
.int#.tEtIte**e*ittEtIttEo
*tEtI±I
.

.int#.tEtIte**e*ittEtIttEo
heat heat .
heat heat
zmemylpropom -1-01 zmemylpbpanal Zmethylpbpanoicacid
zmemylpropom -1-01 zmemylpbpanal Zmethylpbpanoicacid

24 Oxidation of Primary Alcohols

As soon as any aldehyde is formed it can be oxidised further by the oxidising
agent, to the carboxylic acid, and so special techniques are needed to stop the
oxidation at the aldehyde stage.

One such method makes use of the lower volatility of the alcohol (due to
hydrogen bonding) compared with the aldehyde. The reaction mixture is warmed
to a temperature that is above the boiling point of the aldehyde, but below that of
the alcohol.

The aldehyde is allowed to distill out as soon as it is formed, thus avoiding any
further contact with the oxidising agent.

Alcohols Marginalizer BilalBilal Hameed

Hameed
 101 11

25 Oxidation Of Primary Alcohols

(b) Apparatus set up for distillation,
producing the aldehyde.

(a) Apparatus set up

for reflux, producing
the carboxylic acid.

If we look at the reactions in terms of changes to the functional groups,

Examiner’s Tip it is easier to generalise the reaction to other molecules:
26 Oxidation Of Primary Alcohols
In organic chemistry, it is
important to focus only on the
changes to a particular functional
group – If
thethe reaction
rest of mixture is heated under reflux, carboxylic acid is obtained as the
the molecule
main product
(the carbon skeleton) should
remain unchanged.
and the aldehyde is not usually isolated.
Thus, if we look at the reaction for another primary alcohol, we get:

However, it is possible to set up the experiment so that the aldehyde is distilled

off as soon as it is formed and before it can be oxidised further.

or
t0H
Tonetti
t0H
Tonetti
or
H+kr20F
c- H Atlcrzoi
'

11 11

c-
H+kr20F
c- H
k H
-7 R
Atlcrzoi -
'
-

11 11

c-
-

heat '
qdistilloffme heat under
.

k -
1
-7
The only change
Productis to H highlighted
R the group - red – the rest of the
in
heat retux
-

1
A heat qdistilloffme
'
under
.

molecule
Productis unchanged. retux
A alcohol aldehyde acid
primary
.

primary
alcohol aldehyde acid .

Here we are using inductive reasoning. We are making the

assumption that, because all primary alcohols we have so far
encountered can be oxidised by potassium dichromate(VI)
to an aldehyde and then a carboxylic acid, then all primary alcohols
will be oxidised in this way. Can we ever know this?

HO
'¥aW
Tara
A

c- c-
OH H
H+/Cr20F Atlcrzoi c-
'

c- Ho OH
c-
1

HO
11 1 11

c-
1

'¥aW
Tara
A A- - A- H -> It -

27 Oxidation OfProduct
Primary Alcohols c- OH
qdistilloffme heat '
heatunder

c- c-
H+/Cr20F 1

Atlcrzoi |
OH
1 '

Ho
1

c-# c-
1 11 1 11

c-
retux
1

H H it
A- - A- H -> It -
μ
heat qdistilloffme
'
heatunder
ethanol ethanol 'd
gthanoicaa
|
1 1

Usingit an excess of oxidising agent#and heating the reaction under

μ reflux to
1

Product retux
.

prevent any escape of the aldehyde

ethanol before distillation, allows the
ethanol alcohol to 'dbe
gthanoicaa
.

oxidised all the way to the carboxylic acid.

This oxidation reaction can be used to distinguish between primary, secondary

and tertiary alcohols.

on c- H
11

c-
OH

ttlcrzittgheatunderreinx
R -> R

:
-
-

on
I HYMNOI tgheatunderrtux
H

c- Halum
11

c-
OH

ttlcrzittgheatunderreinx
R
primary
-

-> R -

I HYMNOI tgheatunderrtux
H

alum
primary

÷r
Hu
c-
tkrzittgheatunderreinx
11

c-
,

=> 12
'
R -

R R -

1
HYMNOI tgheatunderrtux

c-
H
BilalBilal
HameedHameed Marginalizer Alcohols
tkrzittgheatunderreinx
11

c-
,

=> 12
'
R R H H H 0 R -

c-
-

OH
HYMNOI tgheatunderrtux
c- C- c- c-A
1

H A- out my H -
 12 102

on
28 Oxidation Of Secondary
Htkrzoi Alcohols
Htkrzoi
' '

c- H
secondary 11

c-
- - ketone OH

ttlcrzittgheatunderreinx
R -> R

:
alcohol heat heat
-
-

Secondary I HYMNOI
alcohols are also oxidised by heating with acidified potassium
tgheatunderrtux
H
dichromate(VI)
alum
(or acidi ed potassium manganate(VII)).
primary

They are oxidised to ketones, which cannot be oxidised any further.

Htkrzoi Htkrzoi

Ot
' '

" secondary - ketone -

alcohol Htkrzoi
heat Htkrzoi
heat
' '

ftp.eptttt#IinPHEPFt
' secondary Htkrzoi- Htkrzoi
' '

secondary ketone -
alcohol -heat ketone heat
-
alcohol heat heat

÷r
Hu
c-
Ot
"
-2-01 propanone 11
pnpan
tkrzittgheatunderreinx
ftp.eptttt#IinPHEPFt
'

HYMNOI c-
Ot
,

=>
' " R 12
R R

Ot
-
-

"

ftp.eptttt#IinPHEPFt
'
1
tgheatunderrtux
ftp.eptttt#IinPHEPFt
'
H
-2-01 propanone
pnpan

)CHzt[o]
-2-01 0
CHZCHCOH H H
secondaryCHZCOCHZTHZO
pnpan propanone H

Htkrzoi c-
Htkrzoi Htkrzoi

OH
' '

C-
-2-01 propanone
pnpan Htkrzoi
c- out c- c-A
ketone
' '

- -
secondary alcohol heat heat
A-
my ketone - H -
-

alcohol heat heat

CHZCHCOHH -
)CHzt[o] A
CHZCOCHZTHZOH H

CHZCHCOH )CHzt[o] CHZCOCHZTHZO

29 Oxidation Of Secondary Alcohols
)CHzt[o] "'
propan -2-01

Ot
CHZCHCOH CHZCOCHZTHZO pnpanone
OH
ftp.eptttt#IinPHEPFt
Ot
"
0

' Htkrzont
ftp.eptttt#IinPHEPFt
'
OH 0 11
c- '+ -
Htkrzont c-
11 c- C
OH -2-01 0
propanone
heat
c-
I
pnpan
+ - c- c- C

OH'I
heat
Htkrzont 11
0
H' H-2-01
pnpan
c- + - c- c-
propanone
C
I Htkrzont
heat 11
c- + - c- c- C
H heat
CHZCHCOH
I )CHzt[o] CHZCOCHZTHZO
H

11
CHZCHCOH
H OH )CHzt[o] CHZCOCHZTHZO
H 0

11
c- it Httcrzof 0 c-

c- 11
H OH
I
H I I I I I I

11
Ic- I

11
c-c-
H
c-
H
c-
OH

c-I it c-
0

11
A- CHZH CHZH it
c-
OH A- e -

- e 0
-

I I I I
Httcrzof
I I I I

c- c- c- Httcrzof
I
Httcrzof
c- c-c- it
heat I I1

c- c- c- c-
'

11
1
Htkrzont 1
1
11 1

H e OH CHZH H CHZH
A-
CHZH it it A- A- 0
CHZH

11
A- -
e
e c- -+ e C
-

A c-
-

H - H c-
- -

H heat H H H
I I heat I I1
heat I I I

c-
I

c- H
1 1

c-
1
1
1 1 1
A CHZH
1
CHZH
1
A- OH
it H e H
-

H H- A- H 0 e -

H H it
H A
1 1
H H ' heat
Htkrzont 1 11 1 1 H H
Zmethylbutan -2-01+ 3-c-methyl butanone
c- C H
H A H H c- - H H
I heat
Zmethylbutan -2-01 3- methyl butanone
HOH

11
H H 0
butanone

11
Zmethylbutan I-2-01
Zmethylbutan
-2-01
I I c- it
I 3- methyl
3- methyl
Httcrzof butanone
I I I
c- it
A-
c-
1
e
1
-

c-
CHZH
heat
- A-
c-
1
e -

c-
CHZH
1 1

H A H H H H H

11
H OH H 0

11 ?
30 Oxidation c-HitAlcohols
Of Tertiary c-

c-
I I I I I
Httcrzof I I

c- c- OHc-
c- methylCHZH
c-
OH H
Zmethylbutan butanone it -2-01 3- e
A- CHZH A-

u
e -

- -

Htkrzont
CHZH
1

c-
heat
1 1

c-
H 1 1
H 1 1 1

H H noreaction

u
Tertiary alcohols do not oxidise.
CHZH ?
-

H A H H 1 1 1
Htkrzont H H H
noreaction

c-
H H

c-H
-

H t OH H

?
u
-2-01-2-01 Htkrzont

CHZH
1

c-
1

Zmethylpwpan
1

3- methyl butanone

c-
Zmethylbutan
H t
OH
H H noreaction

u c-
-

c- ?
Zmethylpwpan -2-01
Htkrzont
CHZH
1 1 1
H OH H
t

u
H H noreaction
CHZH ?
Htkrzont
-
1 1 1

Zmethylpwpan H -2-01
-

H noreaction

t t

Zmethylpwpan -2-01
Zmethylpwpan -2-01

c-
c-
H OH H

u ?
Htkrzont
CHZH
1 1 1

H -

H noreaction

Zmethylpwpan -2-01

Alcohols Marginalizer BilalBilal Hameed

Hameed
 103 13

::
31 Oxidation Examples
c-
H H H
cites
I I H+/KzCrz0y

'T d- c- H -
* -

heatunarrlmx
c-
,
H cites
H bit H 'oH
I I H+/KzCrz0y

'T d- c- H -
* -

, heatunarrlmx
bit 'oH

:
c-
H H H
cites
I I H+/KzCrz0y

'T d- c- H -
*

::
-

, heatunarrlmx
bit 'oH

c-
t H H
CH3 H+/KzCrzOy
, 1

+1¥ - d- c- H -

c-
t
CH3
1 H
by H
fμ H+/KzCrzOy
, 1

+1¥ - d- c- H -

:
1
by fμ

d- c-
heattgdishlloffpndnct
t H H
CH3 H+/KzCrzOy
, 1

H -
+1¥ - c-

d- c-
H
fμ t H
by
heattgdishlloffpndnct
Atl
1
CHZ
, KMNOY

'T
,
c- H -
* -

heatunarrlmx
d- c- c- Examples
t , H H
Atl bit 'oH
32 it Oxidation
CHZ
KMNOY

'Theattgdishlloffpndnct
, ,
OH
H -
* -

heatunarrlmx ,
bit 'oH

c-
t H H
it CHZ
OH , Atl KMNOY
'T
,
* - d- c- H -

, heatunarrlmx
bit 'oH
it OH

"

:
c-
IItE¥#E¥I
H H H
cites
I I H+/KzCrz0y

'T d- c- H -
* -

heatunarrlmx

#
,
bit 'oH

:
c-
t H H
CH3 H+/KzCrzOy
, 1

+1¥ - d- c- H -

1
by fμ

33 Alcohols From Carbonyls (Reduction)

heattgdishlloffpndnct
Reagent t c- c- borohydride,
H
sodium NaBH4(aq) or lithium
H
Atl KMNOY CHZ
,

'T d- aluminiumhydride,
,
H -
*
LiAlH 4, in ether.
-

heatunarrlmx ,
bit 'oH
Condition
it OH heat

Type Reduction
Alternate hydrogen gas over a nickel or platinum catalyst and heat
Aldehydes give primary alcohols, while ketones give secondary alcohols.

!
' '
RCHO +2ft ] => RCHZOH RCOR +2ft ] -7 RCHCOHK

0 0
"
Red
" 1

H OH '
OH '
Rt -

-> H -

R -

C -
R -> Re R -

Ctbutzt
utzatzt
ctbutzt
-
0 0
" " 1
H OH OH
-

- H CHZ CHZ
->
- -

I pnpomtol baton -2-01

1
pnpanal bntananonl
H H

BilalBilal
HameedHameed Marginalizer Alcohols
H 0 H H 0 H H

Ctt c- c-
d- OH
11

c-
1 11 1

c-
1

c-
1 1 1

H -
-> H - H
H - A A -

d- -
H
 14 Rt
Rt"
0"
0

-
-

104
H
H ->
->
Red H
Red
OH
OH

H
-

-
-

-
R -

R
0
" 0
C
-
!! " R
-

C -
'

R
'
->
->
Re

H
OH
1

R
-

34 Primary Alcohols From Aldehydes

!Utzutzt
Ctbutzt
utzatzt
ctbutzt
-
0 0

Utzutz
"

Ctbutzt
utzatzt
"

ctbutzt
-
' ' 1
0 OH
RCHO +2ft ] => RCHZOH RCOR +2ft ] -
H -7- RCHCOHK
H -
0 CHZ
-

->
O
" I pnpomtol " 1
pnpanal
H OH bntananonl CHZ
- H
H
-

-> H
- -

pnpanal I pnpomtol bntananonl

0 0 H
"
Red
" 1

H OH '
OH '
Rt -> H R C R -> Re R

OHH
- - -
- -

H 0 H H 0 H

Ctt
11
H
c-
OH c-
c-0 d-
1 11

c-H A

OHH
1

c-H
- 1 1

-> H H
H H
- -
H H -

0 A -

H Ctt c- c-
d-ItOH
I I I 1 I
11

c-
1 11

c- A
1

c-
1 1

H H H
H -> H H
- -
H -

ethanol
I ethanol
I I I
popanone 1 p
H It

Utzutzt
H H H

Ctbutzt
utzatzt
ctbutzt
-
0 ethanol
0 ethanol
popanone

!
" " 1
H OH OH
- H ' CHZ CHZ'
+2ft ]
-

->
RCHO +2ft ] RCHZOH RCHCOHK
- -

=> RCOR -7
I pnpomtol baton -2-01
1
pnpanal bntananonl
H H

35 Secondary0 Alcohols FromEE

Ketones
H
0
"
Red
OH
,+Li¥# " H -

He OH ' heat
1

OHH
'

Rt H H R C R Re H R
EE
-> 0 H ->
- - -

H
H H
-

0
-

c-
He
H

Ctt
H

H -

c-
1 11

-> H -
c-
d- OH
1

H
-

H -

c-
1 11

c- A
1

H -

A H -

d- ct
heat
,+Li¥#
1 1

-
H
I I I 1 I I I I
H H
H H It H H H H H

ethanol ethanol propan -2-01

popanone

Utzutzt
Ctbutzt
utzatzt
ctbutzt
-
0 0
" " 1
H OH OH
-

- H CHZ CHZ
->
- -

I pnpomtol baton -2-01

1
pnpanal bntananonl
H H

H -

He EE
H ,+Li¥#
heat

OHH
H 0 H H H H 0 H H

Ctt c- c-
d- OH
11

c-
11 1

c- A
1

c-
1 1 1

-> H - H
H -
A -

d- ctI -
H

H H
I I

It
36 AlcoholsH FromHAlkenes 1 I
H
I I

H H

ethanol ethanol Alkenes react withpopanone

acid catalyst and steam at temperatures of around 350oC
propan -2-01

and pressures over 100 atm to form alcohols.

Reagent Steam and dil phosphoric acid (H3PO4)

Condition 350 oC and 100 atm
Type Electrophilic addition
CHECK + Ha CHZCHZOH

He EE
H
ethene ethanol

H ,+Li¥#
1¥
-

heat
H H
ice + to

-
OH

Cfa
fHz
Hf ,

μ
+ HZO
Alcohols Marginalizer BilalBilal Hameed
Hameed
CHZCH =
CHCHZ
 105 15

.IT#.He..ftoIIrwwMf*is:.:..tBi
37 Alcohols From Halogenoalkanes
Hydrolysis of halogenoalkanes via NaOH (aq) produces alcohols.

Reagent Aqueous sodium (or potassium) hydroxide.

Condition heat under reflux in aqueous solution
Type nucleophilic substitution

=~
Ator Htbr
Br H OH H
^

↳
SN
I
SNZ
c-
I

c-
I
,
A-
c- d-
-> It -

1 1
heat 1
/
energy H energy /
A H H

reaction
pathway action
pathway

4,1£ a
0¥
H It
•

pair of electrons
1
tnqmescjisrwbmd
38 Alcohols FromA Halogenoalkanes
,

C C A -
-
-

sport
C Br
μ
-

CH3CHzBr + NNOH - CH3CHzOH NABR

+

CH3CHzBr + OH - CH3CHzOH+ Bt
-

transition OH
-

" "4 ÷PHf

H H H H

C- C- C-

profits
1 1

reactant
1 1

^
It - C -
H 7 It - H
Br
3r . H OH

bimolecular -
two molecules

39 Tests Forinvolved
Thedetermining
Presence
rate step
of 'OH’ Group
-
; the

1. With phosphorous pentachloride, PCl5, gives white fumes (of HCl)

msn.mn?.!YnYiEgHpHt.+t.oItrtI*f.I#Inttw
CH3CH2OH + PCl5 ⟶ CH3CH2Cl + POCl3 + HCl

2. With sodium, gives out bubbles of gas that gives a pop sound with
a lighted splinter (hydrogen).

CH3CH2OH + Na ⟶ CH3CH2ONa + ½ H2

BilalBilal
HameedHameed Marginalizer Alcohols
 16 106

40 Tests to Differentiate Between Alcohols

si
÷
°j÷
St

EL
Warm the alcohol with acidified sodium dichromate.hydrogen
If thebondorange color of
s+H
CHZ

dichromate turns green, distill off theo/Hs+

jH2\=H\gH⇐
product and then warm it with Fehling’s
...

solution.
Tertiary alcohol: The orange color remains unaffected.
Secondary alcohol: The orange color turns green but Fehling’s solution is
unaffected.
Primary alcohol: The orange color turns green and with Fehling’s gives a brick-

Ctt
Hs+
red precipitate.
YHHOE
H2 -

CH3

of
be,tt%QF_# of Fehling’s solution. The result
hydrogen bond
,

Note: Tollen’s reagent can also used instead

-

CHZ CHZ
would be a silver mirror or silver ppt.
-

Htv EY
Hz CHZ CHZ

41 Iodoform Reaction
H '
a
Alcohols that contain the group CH3CH(OH)-, that is, those that have a methyl group
and a hydrogen atom on the same carbon atom that bears the OH group, can be
oxidised by alkaline aqueous iodine to the corresponding carbonyl compound
CH3C(O)-, which is further oxidised a salt of a carboxylic acid (with one less carbon)
and a pale yellow ppt of tri-iodomethane.
μ
CHZCHZ -

g- CHZ §tHz CHzCHz-§tIs

IZTOHTAQ )
#
CHZCHZ CHzCHz
-
§-5 OH
'

-
+ CHI
,

The overall reaction is:

CHZCHCOH ) CHAO
- -

Hutti
42 Iodoform Reaction t ,
OH
It
Except for ethanol, all the alcohols that undergo this reaction are secondary
alcohols, with the OH group on the second carbon atom of the chain, that is,
they are alkan-2-ols.

Alcohols Marginalizer BilalBilal Hameed

Hameed
 107 17

43 Iodoform Reaction

μ
§tHz CHzCHz-§tIs CHzCHz
§-5
The exception, ethanol, is the only primary alcohol to give the pale yellow
precipitate
) of tri-iodomethane (iodoform) with alkaline aqueous iodine:
g- CHZ #
IZTOHTAQ OH
'

ZCHZ -

CHZCHZ -
-
+ CHI
,

CHZCHCOH ) CHAO
- -

44 Skill Check
Which of these alcohols will undergo the iodoform reaction?

Hutti t ,
OH
It

BilalBilal
HameedHameed Marginalizer Alcohols
 18

Alcohols Bilal Hameed