65

17 Hydroxy compounds

17.2 Phenol

PHENOLS

CEDAR COLLEGE PHENOLS

 alcohols
(ii) suggest characteristic distinguishing reactions, e.g. mild oxidation
c) deduce the presence 66 of a CH CH(OH)– group in an alcohol from its
3
reaction with alkaline aqueous iodine to form tri-iodomethane

17.2 Phenol a) recall the chemistry of phenol, as exemplified by the following

reactions:
(i) with bases
(ii) with sodium
(iii) with diazonium salts (see also Section 20.1)
(iv) nitration of, and bromination of, the aromatic ring
b) describe and explain the relative acidities of water, phenol and
ethanol

40 www.cie.org.uk/alevel Back to contents page

CEDAR COLLEGE PHENOLS

 oxidising agent such as acidified
ORGANIC CHEMISTRY
potassium dichromate(VI):
67

substitution reactions CH3

Table 25.5 Orientation in some electrophilic Reaction Percentage of product
COOH Ratio
(ortho + para)
ortho meta para
meta
(1,2) (1,3) (1,4)

CH 3 CH 3 33 1 66 99 : 1

+ 3[O]
PHENOLS + Br2 Br
+ H 2O
OH OH 50 1 49 99 : 1

A phenol group is an —OH group attached directly to a benzene ring.

+ HNO 3 NO 2

24.3 Phenol
The C—O bond in phenol is very strong, as a result
NO
of the delocalisation
NO 6
of
93.5
the lone
0.5
pair
21 : 14
of 2

electrons on oxygen over the arene ring. There are no reactions

+ HNO NO
in which it breaks, unlike 3 2

Phenol, C6H5OH, is a crystalline solid which melts at

the situation with the alcohols. CO 2 H CO 2 H 19 80 1 1:4

43 °C. It is used to manufacture a wide range of products + HNO 3 NO 2

However–OH group in phenol undergoes a variety of reactions.

(Figure 24.5). It’s structure is:
chain is oxidised to form a carboxylic
chain is oxidised
acid. For
to form
example,
a carboxylicTh acid. For example,
e melting point of phenolThise
The data in Table 25.5 can be interpreted as follows.

methylbenzene produces benzoic methylbenzene

acid whenproduces
refluxedbenzoic
with acidcompound
when refluxed
of itswith
molecularcom
mas
● The orientation of the incoming group (NO2 or Br) depends on the substituent
OH ●
already in the ring, and not on the electrophile.
Some substituents favour both 2- and 4-substitution, whereas other substituents
alkaline potassium manganate(VII) alkaline potassium
or anothermanganate(VII)
strong orbonding
anotherbetween
strong its molecules.
bond
H
O favour 3-substitution, at the expense of both 2- and 4-substitution.

oxidising agent such as acidifi
If we look closely at the types of substituents that are 2,4-directing, we find that
oxidising
ed agent such as acidified non-polar benzene ring makes nonp
either they are capable of donating electrons to the ring by the inductive effect, or
they have a lone pair of electrons on the atom joined to the ring. This lone pair

potassium dichromate(VI):potassium dichromate(VI): soluble in water as it disrupts

Figure 25.12 Delocalisation of the lone pair
in 2,4-directing substituents
solu
hy
can be incorporated into the π system by sideways overlap of p orbitals (see
Figure 25.12).

CH3 CH
COOH water
COOH molecules.
1
joined wate
On the other hand, all those substituents that favour 3-substitution have a δ+ atom
directly to the ring (see Table 25.6).
3
26_12 Cam/Chem AS&A2

Barking Dog Art

the benzene ring Phenol is weakly acidic, losin
Table 25.6 Substituents and their effects on

CH 3 Ar
Ph
2- and 4-directing substituents 3-directing substituents
O

+ 3[O] ++ 3[O]
HO hydroxyl+ group:
HO hydr −
N Ar
2 O 2
δ–

C6H5O−(aq
O
C6H5OH(aq) C6
•
•

H O Ar δ+
C Ar
H
phenoxide ion

24.3 Phenol 24.3 Phenol

δ– δ+
N C Ar
•
•

H2 N Ar

The position of this equilibrium

The δ–
O
δ+
C Ar

Phenol, C6H5OH, is a crystalline Phenol,solid

C6H which
5OH, melts
ACID isNATURE
a crystalline
at solid which melts
left-hand at
side. However, pheno
left-h R

43 °C. It is used to manufacture 43 °C.a It

wide
is used
range
toof
manufacture
products a wide range
than of products
water or an alcohol. Th
than
ev
Phenol behaves as a weak acid. The aqueous solution has pH of around 5 or 6. (Ka of the
(Figure 24.5).acid
It’sisstructure (Figure
1.3 x 10—10).
is: 24.5). It’s structure is: Table 24.3. Remember: theTabl hig
weaker the acid (see page 305).
weak
428
OH OH
⇌ + H+
181333_25_A_Chem_BP_415-439.indd 428 10/10/14 8:33 PM

DissociationWe in Weak acid

C6H5OH(aq)phe phenol
The position of this equilibrium lies well over to the left-hand side. However, phenol is
Figure 24.5 Araldite adhesive, compact discs and TCP antisepticCare all −
6H5O (aq)
still a stronger acid than water or an alcohol.
manufactured using phenol as a starting material.
This is shown by its small Ka value. water H2O(l) wat
+
H (aq) + OH
ethanol 2 C2H5OH(aq)eth
Fact file C2H5O−(aq)
In the 19th century phenol was the first antiseptic to be used in
Table 24.3 Comparing the acidity Table
of ph
surgery by Joseph Lister. Many people used to die when their
wounds became infected after an operation. However, when Lister
CEDAR COLLEGE Phenolwards
sprayed the operating theatre and recovery is more acidic than water
PHENOLS
with phenol Phen
least
death rates were dramatically reduced. acidic of
Nowadays, the three compoun
derivatives least
 water 2O(l)
Hbreaks, 14.0
unlike the situation with the alcohols (see H +
(aq)
section +
+ OH
H16.3).
ethanol (aq) + OH
−−
C(aq)
(aq)
+ − 2H5OH(aq) 16.0
H (aq) +of
Reactions OH the (aq)
O¬H
ethanol bond
ethanol C
C2H5OH(aq) H
2 5 OH(aq) −
C2H5O (aq) +16.0 16.0 +
H (aq)
68 − +
ethanol C2H5OH(aq)
Acidity 16.0 C H − O (aq) + H
+ (aq)
CTable
2H524.3
O (aq)
2 5
+ Hthe(aq)
Comparing acidity of phenol, water and ethanol.
Phenols are more− acidic than +alcohols:
C2H5O (aq) + H (aq) Table 24.3 Comparing the acidity of phenol, water and ethanol.
R O H Table
RO 24.3 HH Comparing the acidity of phenol,
–16 water
–3 and ethanol.
RR OO HH RO H
RO Beyond an Phenol
ethyl is
KKa a==1.0 more
group,
1.0 ××10
the
10–16 acidic
molsize
dmthan
–16mol dm–3–3
of water,
the alkyl with
group ethanol
makesbeing
littlethe
Table 24.3 Comparing the acidity of phenol,
Beyond water group,
an ethyl and ethanol.the size K of than
a = 1.0 ×
the alkyl10 group
mol dm makes little
Phenol is more acidic
least acidic ofwater,
the with compounds.
three ethanol being Wethe can explain this by
difference to the electron-releasing effect.acid
Thus propanoic acid is slightly
Propanoic
, butanoic acidacid, butanoic acid
difference to the least
Phenol is ACID
electron-releasing
acidic
more
stronger
of the
acidic
than
NATURE
three
than
looking
ethanoic
effect.
water,
at the
Thus propanoic
compounds.
acid with
conjugate
(the
We can explain
ethanol
is this
being
–3 bases formed on
electron-releasing
slightly
by right-hand
the
effthe
ect of an ethyl
stronger than ethanoic
looking acid
at (the
the electron-releasing
conjugate bases
××10
–10
formed eff–3ect of an ethyl
–3on the right-hand
Phenol haveisvery
more acidic than O water,
H with ethanol being the
KKa a==1.3 –10mol dm
and O H
all pentanoic acid all have very
OO HHleast acidic of the three compounds.
1.3 10 mol
We
dm
can explain this by propanoic
–10
acid O O HH side Kof
a = the
1.3 × equations
10 mol dmin Table 24.3. Th e phenoxide ion, acid,
Phenol because is more group is slightly
acidic than group
greater
water, is slightly
than
with that of
ethanol greater
a− methyl
being than that
group)
the ofbut
least aacidic
methyl ofgroup)
propanoic the acid,but
three
similar acid strengths of the side of the equations in Table 24.3. Th e phenoxide ion,
leastbecause
ngths acidic of of thethe three compounds. looking We can explain Cthis
6H 5O by (aq),very hasacidits negative thecharge spread over acid the whole
mechanism
which alkyl bycompounds.
groups which alkylbutanoic
The negative groups
(phenol acid
charge of the> anion
water Cat
andcan 6>
the
butanoic
pentanoic
H 5O
−
beethanol
conjugate
acid
(aq), acid
delocalisedhas and
inover all
its
terms
the
bases
pentanoic
have
negative formed
charge
of acidity).
benzene
similaron
all acid
spread
ring. Figure
have right-hand
very similar
strengths.
25.17over the whole
strengths.
looking at the conjugate bases formed
side
whichofthison
can the
the right-hand
equations ion as one of24.3. the lone epairs on the oxygen ion, atom overlaps
donate
ns. This ariseselectrons.
because This
showsarises
various because
ways in ion be of thein
as represented.
one Table
lone pairs on theTh oxygen phenoxide
atom overlaps
re side ofcompact
the equations
The in
phenoxide Table 24.3.
ion, 6HTh5O ewith
Cantiseptic−− phenoxide
(aq), has its with
ion,
negative the delocalised
charge π bonding
spread over system in the benzene
the whole
whole ion as ring.
of
24.5
of the
electron
Araldite
eresentations
adhesive,
adhesive,
overlap
density
compact
ofinand
discs electron
TCP –
discs and
density
antiseptic are inC
TCP
all 6H 5 O (aq),
are allthehas its negative
delocalised π bonding charge spread
system in theover the
benzene ring.
ufactured using −phenol
of the phenol as a starting O material. O O O
C
a 6H
rphenol
C–H 5aO
bond
asor (aq),
(either
starting
C–C) onehasC–H
material.
with ofitsthe
negative
or lone
C–C)pairs charge
with iononasspread
the
one ofover
oxygen the the
atom
lone whole
overlaps
pairs – on with
the the– delocalised
O oxygen atom overlaps π bonding
a p orbital on an 2-Chlorobutanoic
– O acid is a stronger – acid than 4-chlorobutanoic acid.
ion
n adjacent as one atom –theadjacent
ofsystem lone in pairsatom
the on– the
2-Chlorobutanoic
benzene
with oxygen
ring. This acid
atom
the delocalised is a overlaps
makes stronger
the ion acidmore
bonding than stable
system4-chlorobutanoic
inthanthe−an acid. ion.
ethoxide
benzene
discs and TCP antiseptic
-conjugation/hyperconjugation.
hyperconjugation. are all The
The further the Cl is from the COO further π the Cl −is from the COO
group in the anion, the group in ring.
the anion, the smaller
smaller
with the delocalised π bonding system in the benzene ring. –
– CH3CH2 O–
material. the electron-withdrawing CH CH O
Fact file the electron-withdrawing effect–it has on it. effect it has on it. 3 2
O
nrythe 19th was
century –first antiseptic to be used in –
phenol the fiphenol Owas the
rst antiseptic to be used in phenoxide ion, O(–)
ethoxide ion, with
urgery phenoxide ion, ethoxide ion, with
h Lister.by Joseph
Many Lister.
people usedMany people
to die whenusedtheir to die when their with negative CH O– negative charge
3CH2 charge
(–) (–)
with negative negative
wounds
infectedbecame
after aninfected
operation. after
or an operation. However, when Lister
However, when Lister O –
or
charge spread over concentrated on
prayed the operating theatre and recovery wards with CH3CH2 charge
phenol
O spread over the whole ion concentrated on the oxygen
rating theatre and recovery wards with phenol the whole ion (–) the oxygen
death rates
rstdramatically were
antisepticreduced.dramatically
to be used reduced.
in derivatives
Nowadays, Nowadays, derivatives
ofedphenol are used because phenol phenoxide
itself is toxic and caustic. This
This reduces
ion,
delocalisation delocalisation reduces
ethoxide
the charge the
density charge
ion,of the density of the
with
e used to die when their and caustic.
because phenol itself is toxic
Compounds such as phenoxide
h as 2,4,6-trichlorophenol, foundion,
2,4,6-trichlorophenol,
in TCP® and found in TCP® ethoxide with
ion,
andnegative withnegative
negative
charge charge on ion
on the phenoxide the phenoxide
negative
comparedcharge ion compared with
with
eration. However, when Lister charge
−
spread
or C2OHover −−
H5O(aq)(aq).orTh
Cerefore − +
concentrated
2H5O (aq). Thions on
erefore
are H
+
not(aq) ions are not
Dettol®, without
bacteria the with
still kill bacteria negative
nastywithout 26_17
the Cam/Chem
side-effects nasty side-effects
of phenol. negative
AS&A2 of phenol.OH (aq)charge 3 H (aq)
covery wards charge with phenol
spread overDog Art
Barking
the whole
concentrated
as strongly on ion
as strongly
attracted to theattracted
phenoxidetothe
433oxygen
the
ion phenoxide
as they are toion as they are to
the
d. Nowadays, derivatives whole ion the oxygen
self is toxic and caustic.
This delocalisation reduces the charge density
24 Benzene and24
of the
its compounds 379
Benzene and its compounds 379
This delocalisation
433
reduces the charge
negativedensity
charge of
on the
the phenoxide ion compared with
10/10/14 8:33 PM

henol, found in TCP® and

negative charge on the phenoxide OHion
− compared with
(aq) or C2H5O−(aq). Therefore H+(aq) ions are not
nasty side-effects
− of phenol. −
withOH blue(aq)
Phenol or and
reacts
litmus C 2H5O (aq). Therefore
with blue litmus andas strongly H+(aq) ions aretonot
attracted the phenoxide ion as they are to
forms
as strongly
h sodium salts with sodium hydroxide.
attracted to the phenoxide ion
hydroxide. as they are to
is still however a weakerThe dissociation of The dissociation
phenol may be of phenol
shown as:may be shown as:
er aIt weaker
acid than 24 Benzene and its compounds 379
boxylic acids.carboxylic acids.C6H5OH C6HC O6H
− 5OH
+ H + C6H5O− 379 + H+
Phenol mayfrom be distinguished24 fromBenzene and its 5 compounds
ACID NATURE
distinguished
s bycarboxylic
the fact thatacidsit by the factor,
that it
showing or, showing structures:
structures:
The dissociation of phenol may be shown as:
e COwill2 not sodiumCO2 from sodium
fromliberate
natehydrogencarbonate
solutions, i.e. it solutions, i.e. it
d thana carbonic
is weaker acid acid.than carbonic acid.

Phenolinissodium
soluble more soluble in sodium
hydroxide solution
ion than in water. It than in water. It
reacts hydroxideThe dissociation
with the sodium of ethanol is: The dissociation of ethanol is:
hydroxide
sodium The dissociation of ethanol is:
to form +salt (C6H5O−Na+)
c salt (C6Han 5O ionic
−
Na )
hereand
aretherefore
stronger there are stronger
interactions
th water with water molecules.
molecules.

Again the
Again we will consider we stability
will 4consider
of thethe stability of the base.
anion/conjugate anion/conjugate
The base. The
−
lone pair on the Olone
−
inpair
the on the O in
phenoxide ionthe phenoxide
overlaps with ion
the overlaps
delocalisedwith the delocalised
system
system in the benzene in the
ring benzene
(Figure G31).ring
This(Figure
spreadsG31). This
out the spreads out the negative
negative
charge in the ion. The O is thus less negative
+
charge in the ion. The O is thus less negative and the H is not attracted and the H+ is not attracted
backanion
back as strongly. The as strongly.
is thus The anionand
stabilised is thus stabilised
phenol and phenol
is a stronger acid is a stronger acid
than ethanol. In ethanol this delocalisation does not occur and indeed occur
than ethanol. In ethanol this delocalisation does not the and indeed the
CEDAR COLLEGEnegative charge on negative
the O in charge on the Oion
the ethoxide in isthe ethoxidebyion
increased theiselectron-
increased byPHENOLS
the electron-
donating alkyl group.
donating alkyl group.
 Acidity
Phenols are more acidic than alcohols:

69 R O H
RR OO HH
RO
RO
RO
H
HH K a = 1.0
KKa a==1.0
××10
1.0×
–16
–16 mol dm–3
–16
1010 molmoldm
dm
–3
–3

–10 –3
O H O H K a a==1.3 ××10 –10mol dm–3–3
OO HH KKa = 1.3× 1010 mol moldm
dm
–10
OO HH 1.3

The negative charge of the anion can be delocalised over the benzene ring. Figure 25.1
ACID NATURE shows various ways in which this can be represented.

Figure 25.17 Representations of the phenol –O O O O

anion
We will consider the stability of the anion/conjugate base. – –

–
The lone pair on the O— in the phenoxide ion overlaps with the delocalised system in the
–
benzene ring. This spreads out the negative charge in the ion. O(–)

(–) (–)
or O or

(–)

The O is thus less negative and the H+ is not attracted back as

26_17strongly. The anion is thus
Cam/Chem AS&A2
433
stabilised and phenol is a stronger acid than ethanol. Barking Dog Art

In ethanol this delocalisation does not occur and indeed the negative charge on the O in
181333_25_A_Chem_BP_415-439.indd 433

the ethoxide ion is increased by the electron-donating alkyl group.

ACID NATURE
The phenoxide ion (C6H5O−) is more stable than the ethoxide ion (C2H5O−) and hence
its formation is favoured.

In the phenoxide ion, the charge is delocalised and is stable. Thus phenol reacts with
alkalis unlike alcohols.

Compound Dissociation in water pKa

phenol C6H5OH(aq) ⇌ C6H5O−(aq) + H+(aq) 10.0

water H2O(l) ⇌ H+(aq) + OH−(aq) 14.0

ethanol C2H5OH(aq) ⇌ C2H5O− (aq) + H+(aq) 16.0

CEDAR COLLEGE PHENOLS

 CH3 COOHCH3 waterCOOH
molecules. water mo
70
Phenol
Phenol is weakly acidic, losing an H+ i
+ 3[O] + H+2O 3[O] hydroxyl group:
+ HO hydroxyl
2

C6H5OH(aq) C6H5O−(aq) +CH +

6H(aq
5O
phenoxide ion
PHENOL IN WATER
3 Phenol 24.3 Phenol
Phenol dissolves very slightly in water to form a weak acidic Th e position
solution. of this
It is a stronger equilibriumTh
acid e posit
lies well
l, C6H5OH,than is aaliphatic
crystallinePhenol,
alcohols. C6H5OH,
solid which meltsisata crystallineleft-hand
solid which side.melts at phenolleft-hand
However, is still a
It is used toThe
manufacture 43 °C. Itrange
a wide is usedofto manufacture athan
products widewaterrangeorofanproducts
ring helps weaken the O-H bond and stabilises the resulting phenoxide ion.
alcohol. The values than wat
of p
e 24.5). It’s structure is: (Figure 24.5). It’s structure is: Table 24.3. Remember: the higher Tablethe24.
v
weaker the acid (see page 305). weaker th
OH OH—
+ H 2O ⇌ + H 3O +

Weak acid Dissociation in water Weak ac

Regular alcohols (aliphatic alcohols) do not react with water to form an acidic solution
phenol C6H5OH(aq) phenol
C6H5O−(aq) + H+(aq)
CHEMISTRY 7 water H2O(l) water
H (aq) + OH−(aq)
+

ethanol C2H5OH(aq) ethanol

Consequently, phenol not only reacts with sodium metal, giving off hydrogen−
(aq) + H+(aq)
C2H5O gas:
OH O Na
Tablewater
Table 24.3 Comparing the acidity of phenol, 24.3
1–
Na H 2 (g)
2

PHENOL IN ALKALIS Phenol is more acidic than water,Phenol with ethis

sodium phenoxide least acidic of the three compounds. leastWe
acidic
Phenols dissolve in aqueous sodium hydroxide:(a white solid)
looking
but, unlike alcohols, it also dissolves in aqueous at the
sodium hydroxide: looking
conjugate bases formed ona
OH O Na side of the equations in Table 24.3. sideThofethp
− −
C6H5O (aq), has its negative charge C6Hsprea
5O (
NaOH ion as one of the lone pairs on the
H2 O ionoxygen
as on
24.5 Araldite adhesive, compactFigure 24.5
discs and TCPAraldite adhesive,
antiseptic with
are all compact discs and
−3
the delocalised
TCP bonding system
antiseptic areπall with thein d
Phenol is visibly acidic: the pH of a 0.1 mol dm solution in water is 5.4, so it will
manufactured
ctured using phenol as a startingturn
material. using phenol
universal indicator as ayellow.
solution startingAnmaterial.
old name for phenol is carbolic acid (see
O –
section 25.6).

Esterification
CH3C
ct file Fact file
Because of the delocalisation over the ring of the lone pair on the oxygen atom,
phenol is not nucleophilic enough to undergo esterification in the usual way, that is,
e 19th century phenol was the fiby In the 19th
rst antiseptic
heating tocentury
with be usedphenol
a carboxylic was
in 8acid thea fitrace
and rst antiseptic to be used
of concentrated in acid (for the
sulfuric
mechanism of esterification, see section 18.3). phenoxide ion, ethox
surgery
ery by Joseph Lister. Many people used bywhen
to die Joseph Lister. Many people used to die when
their with their
negative nega
wounds
nds became infected after an operation. became
However, infected
when Listerafter an operation. However, when Lister O
charge spread over concc
sprayed
yed the operating theatre and recovery OHthe
wards operating
with phenol theatre and recovery wards with the phenol
wholeOion C CH
3
th
death ratesderivatives
h rates were dramatically reduced. Nowadays, were
CHdramatically
3 CO2 H
reduced. Nowadays, derivatives
heat with
H 2O
conc. H SO This delocalisation reduces the charge
2 4 Th is delo
de
henol are used
CEDARbecause phenol itselfofis phenol
COLLEGE arecaustic.
toxic and used because phenol itself is toxic and caustic. esterPHENOLS
Compounds
pounds such as 2,4,6-trichlorophenol, found in TCPsuch
®
as 2,4,6-trichlorophenol,
and negative
found charge
in TCP ® on the phenoxide
and
not formed
negative
ion co
− − − +
® Phenol can, OH
® however, be esterified by adding (aq)chloride:
an acyl or C H OH H
O (aq). Therefore (aq)(a
 71

RGANIC CHEMISTRY
PHENOL WITH SODIUM
Phenol reacts with sodium metal, giving
Consequently, phenoloff
nothydrogen gas:
only reacts with sodium metal, giving off hydrogen gas:

OH O Na

1–
Na H 2 (g)
2

sodium phenoxide
(a white solid)
but, unlike alcohols, it also dissolves in aqueous sodium hydroxide:
OH O Na

NaOH H2 O

Phenol is visibly acidic: the9 pH of a 0.1 mol dm−3 solution in water is 5.4, so it will
turn universal indicator solution yellow. An old name for phenol is carbolic acid (see
section 25.6).

Esterification
Because of the delocalisation over the ring of the lone pair on the oxygen atom,
phenol is not nucleophilic enough to undergo esterification in the usual way, that is,
by heating with a carboxylic acid and a trace of concentrated sulfuric acid (for the
mechanism of esterification, see section 18.3).

REACTION WITH SODIUM O

OH O C CH 3
Phenol reacts with sodium in a similar way to ethanol.heat with
CH 3CO2H conc. H SO H 2O
2 4
Bubbles of hydrogen form when a small cube of sodium is added to molten phenol or to a
ester not formed
solution of phenol in an inert solvent.
Phenol can, however, be esterified by adding an acyl chloride:
The main product of the reaction is sodium phenoxide.
OH O CH3
! CH3COCl
1NaOH C ! HCl
or pyridine
O
phenyl ethanoate

See section 26.3 for a fuller description of the conditions used for this reaction.

Substitution reactions of the benzene ring

As we mentioned on page 428, phenols are more susceptible to electrophilic attack
than benzene, owing to the 10 delocalisation of the lone pair of electrons on oxygen.

This allows phenol to react with reagents that are more dilute, and also to undergo
multiple substitution with ease.

Nitration
When treated with dilute aqueous nitric acid (no sulfuric acid is needed) phenol gives
a mixture of 2- and 4-nitrophenols:
CEDAR COLLEGE PHENOLS
OH OH OH
NO
 72
CHEMISTRY
ORGANIC CHEMISTRY

Consequently, phenol not only reacts with sodium metal, giving off hydrogen gas:
Table 25.5 Orientation in some electrophilic Reaction Percentage of product
substitution reactions

RING
OH REACTIONS
O Na WITH PHENOLS ortho
(1,2)
meta
(1,3)
para
(1,4)

CH 3 CH 3 33 1 66
1–
Na the –OH group to
At first sight we might expect H 2be
(g) electron-withdrawing due to the high
2 + Br 2 Br

electronegativity of O. However, the –OH group also possesses a lone pair of electrons
OH OH 50 1 49
sodium phenoxide
and overlap of this lone pair into the ring activates the benzene ring.
(a white solid) + HNO 3 NO 2

but, unlike alcohols, it also dissolves in aqueous sodium hydroxide: NO 2 NO2 6 93.5 0.5
This π donationOH
into the ring is a bigger
O Naeffect than the electron withdrawing effect (due to
+ HNO 3 NO2

the electronegativity of O). ring more negative, i.e. more attractive towards electrophiles and
NaOH
the reaction occurs more quickly than with benzene.
CO H CO H 2 2 19 80 1
H2 O
Therefore there is net donation of electron density into the ring and the ring will attract
+ HNO 3 NO 2

−3
Phenol is visibly acidic: the pH of a 0.1 mol dm solution in water is 5.4, so it will
electrophiles more strongly. At first sight we might expect the –OH group to be electron-
turn universal indicator solution yellow. An old name for phenol is carbolic acid (see The data in Table 25.5 can be interpreted as follows.
section 25.6). withdrawing due to the high electronegativity of● The
O. However, the –OH
orientation of the incoming group (NO2 or Br) depend
group also possesses a lone pair of electrons and overlap of ring,
already in the thisandlone
not on the electrophile.
Esterification pair into the ring activates the benzene Hring ● Some substituents favour both 2- and 4-substitution, where
(Figure G40).
favour 3-substitution, at the expense of both 2- and 4-subs
O
Because of the delocalisation over the ring ofThis
the πlone
donation
pair onintothe theoxygenringatom,
is a bigger effectIf we
than the -withdrawing
look closely at the types of substituents that are 2,4-d
effect (due to the electronegativity
phenol is not nucleophilic enough to undergo esterification in the usual way, that is, of O). Therefore
either there
they areiscapable
net of donating electrons to the ring by
donation
by heating with a carboxylic acid and a trace of electron
of concentrated sulfuricdensity
acid (forintothethe ring they
and have a lone pair of electrons on the atom joined to th
the ring will
can be incorporated into the π system by sideways overlap
Figure 25.12 Delocalisation of the lone pair
attract
mechanism of esterification, see section 18.3).
11
electrophiles more strongly.
in 2,4-directing substituents
Figure 25.12).
On the other hand, all those substituents that favour 3-sub
O
26_12 Cam/Chem AS&A2
joined directly to the ring (see Table 25.6).

Table 25.6 Substituents and their effects on 2- and 4-directing substituents 3-directing substi
OH One particularly the Barking Dog Art
good example
Oring C of CH
benzene the 3ease of reactivity
CH Ar
of phenol is in its O
3
heat withreaction with chlorine.
CH 3CO2H conc. H SO H 2O −
N Ar
2 4
Phenol reacts with chlorine water – Cl2(aq) – to form O
Phenol is also made more reactive
2,4,6-trichlorophenol (noester not formed
halogen carrier required): δ–
O

•
•
in water since it is acidic and H O Ar δ+
C Ar
Phenol can, however,
produces the phenoxide ion be esterified by adding an acyl chloride: H

C6H5O−. The negative

OH charge O CH3
δ–
N
δ+
C Ar

•
•
H N Ar 2
on the O means withdrawal 1NaOH C
! CH3COCl or pyridine ! HCl δ–
O
is reduced and donation is δ+
C Ar
increased, therefore the ring is O
RING REACTIONS WITH PHENOLS
more attractive to electrophiles. phenyl ethanoate
R

See section 26.3 for a fuller description of the conditions used for this reaction.
Phenols are more susceptible to electrophilic attack than benzene, owing to the
Substitution
delocalisation reactions
of the lone pair of the
of electrons benzene ring
on oxygen.
As we mentioned on page 428, phenols are The NOsusceptible
more 2 group is electron-withdrawing
to electrophilic attack and deactivates the benzene
than benzene, owing to the delocalisationring.
of the loneless
With of428
pairelectronelectrons
density on in
oxygen.
the to
ringundergo
it attracts multiple
electrophiles less
This allows phenol to react with reagents that are more dilute, and also
This allows phenol to react with reagents strongly,
that are more dilute,
therefore and also to reacts
nitrobenzene undergo more slowly than benzene. NO2 is
substitution withsubstitution
multiple ease. with ease. electron-withdrawing because 428
181333_25_A_Chem_BP_415-439.indd of the high electronegativity of the atoms
Nitration in the group and, unlike the O in phenol, it does not possess a lone pair
When treated with dilute aqueous nitric acid (no sulfuric
of electrons on theacid is can
N that needed) phenol
be donated gives
into the ring.aThere is also
When treated with dilute aqueous nitric acid (no sulfuric acid is needed) phenol gives
mixture ofa 2- and of4-nitrophenols. delocalisation of the electrons from the ring onto the NO2 group.
mixture 2- and 4-nitrophenols:

OH OH OH
NO2
The position of substitution is determined by the charge distribution in
the intermediate. The more stable the intermediate the more likely it is to
dilute HNO 3at room temperature
be formed.
This is most usually explained using the Kekulé structure of benzene
50% NO
but to understand the explanation we 2must first understand something
about resonance. 50%

Two
12 possible Lewis structures may be drawn for benzene, with the
double bonds between different atoms (Figure G41). These are called
resonance structures. The actual structure of benzene is regarded as a
resonance hybrid of these two structures – not one or the other but
39.indd 434
somewhere in between. 10/10/14 8:33 PM

The position of substitution in nitrobenzene can be explained in terms

CEDAR COLLEGE PHENOLS
of the stability of the intermediate carbocation formed.
 73

25 RING REACTIONS WITH PHENOLS

Arenes and phenols
25 Arenes and phenols
Phenol decolorises a dilute solution of bromine in water at room temperature, giving a
Bromination
white precipitate of 2,4,6-tribromophenol.
Phenol Noofaluminium
decolorises a dilute solution
Bromination bromide
bromine in water is needed.
at room temperature, giving aContrast this

si
white precipitate of 2,4,6-tribromophenol. No aluminium bromide is needed. Contrast
with the conditions needed forconditions
this with the the bromination
Phenol decolorises of benzene.
a dilute solution of bromine
needed for the bromination
in water at room temperature, giving a
of benzene on page 423.

÷
white precipitate of 2,4,6-tribromophenol. No aluminium bromide is needed. Contrast

°j÷
St

EL
OH the conditions needed for the
this with OHbromination of benzene on page 423.

s+H
CHZ

(aq) o/Hs+
bond
OH Br OH Br hydrogen

3BrjH2\=H\gH⇐
2
Br Br ... 3HBr
3Br2 (aq) 3HBr
Br
Br chlorine water on phenol, is used in dilute
A similar product, formed by the action of
solution as product,
the antiseptic TCP (see page 436).
A similar product is formed by
A similar the action
formed byof
thechlorine
action water
of chlorine on
water on phenol.
phenol, is used in dilute
solution
OHas the antiseptic TCP (see page
OH436).
OH Cl OH Cl
3Cl2(aq) Cl Cl 3HCl
3Cl2(aq) 3HCl

Ctt
Cl

Hs+
YHHOE
H2 -

CH3

of
#
,tt%QF_
Cl
2,4,6-trichlorophenol
(TCP) hydrogen bond
,
2,4,6-trichlorophenol
13 (TCP)
-

Coupling
CouplingCHZ CHZ -

Phenols couple with diazonium salts (see section 27.3) to form azo dyes:
Phenols couple with diazonium salts (see section 27.3) to form azo dyes:
OH
N
N1 N N OH
OH
aqueous NaOH at 5 8C
N1 1 OH 1
N N
(2H
aqueous ) at 5 8C
NaOH
1 N
(2H1)
phenyldiazonium ion an azo dye

phenyldiazonium ion an azo dye

A specific test for phenols
A specifi c testof for phenols

Htv EY
When a dilute solution iron(III) Hz to a dilute solutionCHZ
chloride is addedCHZ of a phenol,
a coloured complex
When a dilute is formed.
solution The colour
of iron(III) depends
chloride ontothe
is added substituents
a dilute solutiononofthe ring.
a phenol,

H IODOFORM REACTIONa
With phenol itself,
a coloured complexa purple coloration
is formed. is observed:
The colour depends on the substituents on the ring.
'
With phenol itself, a purple coloration is observed:

OH O
Alcohols that contain the group CH
OH3CH(OH)-,
Fe 3
that is, those that have a methyl group and a
O Fe
3 (aq) (aq) 3H (aq)
Fe that
3 carbon(aq)atom Fe 3
3H (aq)can be oxidised by
hydrogen atom on the same (aq) bears the OH group,
3
alkaline aqueous iodine to the corresponding carbonyl compound
3
CH3C(O)-, which is
25.6
further oxidised a salt of Some acid
a carboxylic important
(with one phenols
less carbon) and a pale yellow ppt of tri-
25.6 Some important phenols
iodomethane. Antiseptics
A Antiseptics
dilute solution of phenol in water (known as carbolic acid) was one of the
μ
§tHz CHzCHz-§tIs CHzCHz
§-5
A dilute
first solutiontoofbephenol
disinfectants in medicine,
used in water (known as carbolic
by Joseph Lister acid) was oneScotland,
in Glasgow, of the

g- CHZ #
IZTOHTAQ ) disinfectants OH use Scotland,
'

infi1867.
rst to is
Phenol itself beunfortunately
used in medicine, by Joseph
too corrosive to Lister
be of in Glasgow,
general as an
CHZCHZ -

CHZCHZ
in 1867.
antiseptic. Phenol
Many chloro
-

itself isderivatives
unfortunately
havetoo corrosive
been found to be moreof general useantiseptics
potent as an
-
+ CHI
,

H than phenol Many

antiseptic. itself. chloro
They can derivatives
be used have beenlower
in much foundconcentrations,
to be more potent
which antiseptics
reduces
thancorrosive
their phenol itself.
effect.They
Twocan be used
of the most in much lower
common concentrations,(TCP)
are trichlorophenol whichandreduces
their corrosive
chloroxylenol effect.
(see Two
Figure of theThymol
25.19). most common
occurs inare
oiltrichlorophenol (TCP)
of thyme, and is and
an excellent
chloroxylenol
non-toxic (see Figure
antiseptic, as well25.19). Thymol
as being occurs in oil of thyme, and is an excellent
a fungicide.
non-toxic antiseptic, as well as being a fungicide.
435
The overall reaction is: 435

181333_25_A_Chem_BP_415-439.indd 435 10/10/14 8:33 PM

181333_25_A_Chem_BP_415-439.indd 435 10/10/14 8:33 PM
14

CHZCHCOH ) CHAO
- -

Hutti t ,
OH
It
CEDAR COLLEGE PHENOLS
 74

IODOFORM REACTION
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.

15

IODOFORM REACTION
The exception, ethanol, is the only primary alcohol to give the pale yellow precipitate of tri-
iodomethane (iodoform) with alkaline aqueous iodine:

16

CEDAR COLLEGE PHENOLS

 si
75

÷
°j÷
St

EL
s+H
CHZ

o/Hs+
bond
hydrogen
jH2\=H\gH⇐
CHZCHCOH ) CHAO
- -

...

IODOFORM REACTION
Which of these alcohols will undergo the iodoform reaction?

Hutti t ,
OH
It

Ctt
Hs+
YHHOE
H2 -

CH3

of
#
,tt%QF_ hydrogen bond
,

CHZ CHZ -

17

Htv EY
Hz CHZ CHZ

H '
a
IODOFORM REACTION
Carbonyl compounds containing CH3CO- group, that is, those that have a methyl group on the
same carbon atom that bears the oxygen atom, can be oxidised by alkaline aqueous iodine to
a salt of a carboxylic acid (with one less carbon) and a pale yellow ppt of tri-iodomethane.

The tri-iodomethane (iodoform) reaction is thus a very specific test for the CH3CO— group (or
the CH3CH(OH)— group.

μ
- CHZ §tHz CHzCHz-§tIs
IZTOHTAQ )
#
CHZCHZ CHzCHz
§-5 -
OH
'

-
+ CHI
,

The overall reaction is:

18

CHZCHCOH ) CHAO
- -

CEDAR COLLEGE PHENOLS

 76

IODOFORM REACTION
Except for ethanal, all the carbonyls that undergo this reaction are methyl ketones, with the
carbonyl group on the second carbon atom of the chain, that is, they are alkan-2-ones.

The reaction can be use to obtain an acid having one carbon less.

19

IODOFORM REACTION
The exception, ethanal, is the only aldehyde to give the pale yellow precipitate of tri-
iodomethane (iodoform) with alkaline aqueous iodine:

20

CEDAR COLLEGE PHENOLS

 f- b#H
H
CHZ o
77 utz A utz
C- H
I
11 I I

¥
-

¥
-
-

g- H
¥
-

H A H OH B

Zmemylpbpamal memylpropan -1-01

2- 2-
methyl propene
SKILL CHECK 1
Which of these carbonyl compounds will undergo the iodoform reaction? Draw all
the organic products.

ytoweho in
A B C D

21

CEDAR COLLEGE PHENOLS