7

Alcohols, Phenols, and Thiols

Alcohols Contain the hydroxyl (-OH) group. They are
structurally

similar to water but with one of the hydrogens replaced with

am alkyl group. Phenols have a

hydroxyl group directly
attached to aromatic ring Thiols and thiophenols are similar to
an .

alcohols and phenols except the is replaced sulfur.

oxygen by

7.1 Nomenclature of Alcohols

CH3HCH3
CH3OH CH3CH2 CH2 OH OH CH3CH2CH2 CH2 OH

Methanol ↓ -
propanol 2 -

propanol

In-propyl alcohol ( isopropyl alcohol n-butyl alcohol

CH3 CH3
I
CH3CHCH2CH3 CH3CHCH20 H I
CH3 c - Ol
o
-

CH 3
sec-butyl alcohol Isobutyl alcohol

tert-butyl alcohol

7.2 Classification of Alcohols

R
↓

R - C -
OH
R
I
I
R CHzOH R R
-
CHOH

primary (1 % Secondary (2 % (3 %
tertiary

7.3 Nomenclature of Phenols

OH OH Br OH
OH

Br

/
Cl
Br

phenol ↑ - chloropheno .
2 4 , 6-tribromophenol m-hydroxy benzoic acid
 OH
OH

↑
/
CHG
NO 2

P-hydroxybenzaldehyde P-nitrobenzene

7.4 Hydrogen Bonding in Alcohols and Phenols

electron

rich Alcohols form hydrogen bonds With

↑ one another

Rs R RS -

S+
R
S
-

S+
S+ S S+
-
-

O -
H - 0 -
H
O -
H + O -
H
-
~

two Separate a hydrogen bond

[ alcohol molecules

electron poor .

7.5 Acidity and Basicity Reviewed

A bronsted-lowry acid is a
proton donor , Whereas a bronsted-lowry base

is a proton .
acceptor

+
&
-

H-8
3
H- goo + H - : -
It

it
I * s

base acid Conjugate acid Conjugate

of Water base of HC

A lewis acid is an electron pair acceptor; a lewis base is an

electron pair donor

.
Any atom with an unshared electron pair can act

as a Lewis base
. Compounds With an element Whose valance shell is

incomplete also act act as Lewis acids

.
 L
+
t

H + ·j -
H H- " -
H

it
I

lewis H

le Wis
a cid

base

F F

F -
B T
· F -B-
&

i
a

le Wis leXis

acid
base

An amphoteric substance can acts as an acid or as base

.

7.6 The Acidity of Alcohols and Phenols acconois and Phenols are weak acids
.

The conjugate base of an alcohol is an alkoxide ion

.

%
R -

H
R: + H
+

alconol alkoxide
ion

14
Phenols are stronger acids than alcohols mainly because the corresponding

Phenoxide ions are stabilized by resonance.

· j · 0i : 0 : : 0 %
C
R- &
-

-
-

a *

<
E S
>
- -
[

charge delocalized on the

G ↑ La
·
oxygen atom in alkoxide ion

charge delocalized in penoxide ion

# Polar bonds that place a partial positive charge near the negative

Charge On an alkoxide ion stabilize the ion by inductive effect.

&
All electron withdrawing groups increase acidity by stabilizing the conjugate

base
. Electron-donating groups decrease acidity because they destabilize the

conjugate base
.

=
Alkoxides ,
the conjugate bases of alcohols are strong bases just like hydroxide

ion

2 Ro -
H + 2k > 2R : k
+ +
H2
* a

alcohol potassium
alkoxide

R: H
+
Na +
-
H
Na H >

RO -
H +
Sodium
sodium
alkoxide
hydride

B
alcohols cannot be converted to their alkoxides by sodium hydroxide .

because alkoxides are stronger than hydroxide ion however phenols

can be converted to penoxide ions in this way

.

ROH + Na +Ho- , ""RONa + H20

OH +
NaTHO- o -Nat + HOH

Phenol sodium Phenoxide

7.7 The Basicity of Alcohols and Phenols
·
alcohols and phenols function not only as Weak acids but also act as

weak bases .

They have unshared electrons on oxygen and therefore Lewis bases

.

It
I
.
+
R -H + H R -0 -
H
-

alcohol acting alkyloxonium ion

as a base

7.8 Dehydration of Alcohols to Alkenes alcohols can be dehydrated by heating

them With a strong acid .

H , 180
H -

CH2CH2-oh > CH2 = CH2 & H -

OH

ethanol
ethylene

I
It is an elimination reaction and can occur by either an Ed or an EC

mechanism , depending om the class of alcohol-

z
Tertiary alcohols dehydrate by El mechanism
. The first Step

involves rapid protonation of hydroxy group

.

+
+

(CH3lz C-H + H (CH3/zc - - H

it
M
lonization (the rate determining Step 1 With Water as

occurs carbocation
leaving group, readily because the resulting

is tertiary
.

t
*
(CH3) C - -
H (CH3)c + H20
- I
t -
butyl cation
It

#
the proton loss from a carbon atom adjacent to the positive

Carbon completes the reaction

.
 CH3
I CH3
CH2 -
-
C 7 CH2 = C
-
+ H
+

-
CH3 CH3

IIII
The Overall dehydration reaction is the sum of all three

Steps .

H
CH3
I
CHz
- OH It
Heat CH2
-
H-OH
CH2
c
-
= +

I CH3
CH3
isobutylene
t-butylakohol

III
With a primary alcohol, a primary carbocation intermediate is avoided.

The loss of Water and an adjacent proton occurs simultaneously

in an E2 mechanism
.

T
+
CH3 CHeH + H CH3CH2- -
H

it

If + ↓
J
CH2-8 H - CHz =
CH2 + H + H20
CH2 -
-

M I
H

* all alcohol dehydrations begin by protonation of the hydoxyl

group. I alcohol & It S as a base

* the ease of alcohol dehydration is 32 % 10

I/
Sometimes a single alcohol gives two or more alkenes because

the proton lost during the dehydration can come from different

carbon atoms that is attached to the hydroxyl bearing Carbon

.

"In this cases , the alkene With the most substituted double bond

predominates
.

H OH H
I It
11
ChChy
Cha-q
=
and/or
-ChaCHy
CH2- C - CH- C+ 3 CH2 =

heat
I
CH3 CH3 CH3

the major product

7.9 The Reaction of Alcohols with Hydrogen Halides Alcohols react With hydrogen halides

(HCI , HBr , H1) to give alkyl halides

.

'I
Because halide ions are good nucleophiles , we mainly obtain

Substitution products .

>
R - OH + H - X R -
X + H - OH

a lcohol alky
, halide

III/
tertiary alconols reacts the fastest.

>
- room temperature
RT
(CH3/zCOH + H -
C >
(CH3/zC - C + H -
OH
15 mins
t-buty t-butyl chloride
alconol

It
The reaction occurs by an SNI Mechanism that involves a

carbocation intermediate. The final step involves capture of the

t-butyl carbocation by chloride ion .

+ fast
(CH3/zC
-

+ C , (CH3lz(
"Primary alcohols reacts Slowly and must be heated for several hours

With a mixture of Concentrated HC) and a Levis acid Catalyst

such as zinc Chloride .

heat , EnC12
CH3 CH2CH2CH2OH + H -
Cl 7 CH3CHzCHaCHe-C1 + H-OH
several hours

is
↑
the reaction occurs by SN2 Mechanism
. In the first step alcohol

protonated by the acid

.

CH3 CH2CH2CH2 -H +
H
+
CH3ChzCh2Ch2
- -H

it
III
/
In the second step , Chloride ion displaces Water in

typical SN2 process -

CH3 CH2 CH2

- - H
CH3CHzCH2CH2Cl
IIIIC >
H20
-
+
... >
-
HSH
Cl-

14
secondary alcohols react at intermediate rates by both SNd and

SN2 mechanisms .
7.10 Other Ways to Prepare Alkyl Halides from Alcohols

1) alconol converted to a Chlorosulfite ester intermediate .

th e is good leaving
NOW
hydroxide a group.

2) Nucleophilic substitution I can be SNd or SN2) 7

desired
Product

+
C H
G

S i -
II
HCI

i
R C + +
>
-

O
Il heat R - o -
S - a
R OH +
c CI >
-

-
s -

Chlorosulfite ester

thionylchloride Sc
intermediate
they will fly awy ay

#Phosphorus halides also convert alcohols to alkyl halides

.

PX3
3 ROH t 3 3RX + HzP0z(X = C or Br/

Phosphorus
halide

IIII
Both these reactions are mainly With primary and secondary

a Icohols Whose reactions are SIOW .

7.11 A Comparison of Alcohols and Phenols alcohols and phenols have many

similar properties
. But ,

>
It is break of
-

relatively easy to the c-olt bond alcohols

>
-

phenyl cations are

energetically unstable and difficult to form
.

>
Phenols undergo displacement by SN2 Mechanism
-

cannot the

or neither can go replacement of -ou

by an SN1
.
7.12 Oxidation of Alcohols to Aldehydes, Ketones, and Carboxylic Acids

OH
G S
I 11 II
Oxidizing Oxidizing
R - - H -

> R - c -
H R C
- -
& It
>
-

I agent agent
H aldehyde carboxylic

primary alcohol acid

OH O

I II
Oxidizing
Ri R C R
q
R >
-
- -
- -

agent
It Ketone

primary
alcohol

* tertiary alconois having no hydrogen atom on the hydroxyl

bearing carbon do not go these type of Oxidation -

Jones' reagent is an oxidizing agent composed of Cros dissolved

in aqueous H2SO4
. Acetone is used as a Solvent .

It
Cr03
7
Ol O
H +, acetone

(Jones' reagent)

cyclonexano Cyclonexanone

With primary alcohols Oxidation can be stopped at aldehyde

stage by prydinium Chlorochromate (PCC)

G
PCS
CH3/CH2lG CHOH > CH3(CHalG -
H

CH2Cl2 ,
25 °
1 -
octano Octanal
 Preperation of PCC :

& 1
:
-

Y CrOzC
CrOz + HC) + N- I

pridine pridinium Chlorochromate

(PCC)

Oxidation occurs in body :

O
+ Alcohol It
V
CH3CH2OH + NaD CH3) - H + NaDIt
dehydrogenase
ethano acetaldehyde

7.13 Alcohols with More Than One Hydroxyl Group some important polyols :

ethylene glycerol Sorbitol

glycol

CIt 20 H CH20 NO 2

H2SO4
CHO H + 3 HO NO 2 , CHO NO2 T 3H20

CH20H nitric CH2O MOz

acid
glycerol g lycerin trinitrate
 7.14 Aromatic Substitution in Phenols Phenols undergo electrophilic aromatic

under very Mild conditions because oh is ring

- group strongly

activating
.

OH -

OH

+ HONO2 Y +
H20

/
Phenol d inte
NO 2

nitric acid

↑ -
nitropheno

#
Phenols also brominated rapidly With bromine in Water.

Br
OH
OH -
↑
H20
> - Br + 3HBr
+
3 Brz

I
Br

2.
2 416--tribromopheno

7.15 Oxidation of Phenols

OH OH

Naz Cr07
>

HysOn ,
30 %

OH
/
"
colorless yellow
1 , 4-benzene quinone
hydroquinone

7.16 Phenols as Antioxidants Phenols are antioxidants

, preventing oxidation of

substances sensitive to air oxidation .

0 -
H Oa

HO o > + HO -
H
+

hy droxy
radical Phenoxy

radical
 7.17 Thiols, the Sulfur Analogs of Alcohols and Phenols The Sulfhydryl group

-
SH is the functional group of thiols
. Thios are also called

mercaptans ; their Mercury salts are called mercaptides

.

SH

CH3SH CH3 CH2 CH2CH2 SH

methan ethiol 1 butane thiol

↓ hiopheno

2RSH +
AgCl2 > (RS)2 Ag + 2HC/

a mercaptide
III
alkyl thios can be made from alkyl halides by nucleophilic

displacement With Sulfhydryde ion .

Y
-

SH
-

R -
X +
R -
SH + X

·
Thiols are more a cidic than alcohols
. Hence thiols can react With

an to thiolates
aqueous base give .

Nat RS Nat
-

R-SH t OH- > 170H

& sodium

thiolate

1/I
ThiOIS are easily oxidized to disulfides
.

Oxidation
3

2RS -
It RS-SR
reduction
thio disulfide