113

19 Carboxylic acids and derivatives

This topic introduces the chemistry of carboxylic acids and their derivatives

19.1 Carboxylic acids

19.2 Acyl chlorides

ACYL CHLORIDES & ACIDS

CEDAR COLLEGE ACYL CHLORIDES & ACIDS

Cambridge International AS and A Level Chemistry 9701 syllabus Syllabus content

114

19 Carboxylic acids and derivatives

This topic introduces the chemistry of carboxylic acids and their derivatives.

Learning outcomes
Candidates should be able to:

19.1 Carboxylic acids a) describe the formation of carboxylic acids from alcohols, aldehydes and
nitriles
b) describe the reactions of carboxylic acids in the formation of:
(i) salts, by the use of reactive metals, alkalis or carbonates
(ii) alkyl esters
(iii) alcohols, by use of LiAlH4
(iv) acyl chlorides
c) recognise that some carboxylic acids can be further oxidised:
(i) the oxidation of methanoic acid, HCO2H, with Fehling’s and
Tollens’ reagents
(ii) the oxidation of ethanedioic acid, HO2CCO2H, with warm
acidified manganate(VII)
d) explain the relative acidities of carboxylic acids, phenols and
alcohols
e) use the concept of electronegativity to explain the acidities of
chlorine-substituted ethanoic acids

19.2 Acyl chlorides a) describe the hydrolysis of acyl chlorides

b) describe the reactions of acyl chlorides with alcohols, phenols,
ammonia and primary amines
c) explain the relative ease of hydrolysis of acyl chlorides, alkyl
chlorides and aryl chlorides including the condensation (addition-
elimination) mechanism for the hydrolysis of acyl chlorides

19.3 Esters a) describe the acid and base hydrolysis of esters

b) state the major commercial uses of esters, e.g. solvents, perfumes,
flavourings

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

CEDAR COLLEGE ACYL CHLORIDES & ACIDS

 2 3 Reagent Observation with
acidities of alcohols,
acids. Hexanol Phenol Hexanoic acid
Na(s) H2(g) evolved 115H (g) evolved H2(g) evolved
2

NaOH(aq) no reaction Carboxylic

dissolves acids – derivatives
dissolves and further reactions
Na2CO3(aq) no reaction no reaction CO2(g) evolved

26.1 The use of Na, NaOHAtoms and Naor

ACIDITY
groups that draw electrons away from the ¬CO2 group will help the anion −
2CO3
to form,
trate the relative acidities of alcohols, and thisReagent
causes the acid to be more dissociated (thatObservation
is, to becomewith
a stronger
Carboxylic Carboxylic
acids acids
are are
weak weak
acids acids
that that dissociate
dissociate partially
partially in in aqueous
−aqueous
l and carboxylic acids. acid). On the other hand, groups that donate electrons to the ¬CO2 group will Hexanoic acid
Hexanol Phenol
causesolution
solutionthe according
acid to become
Na(s)
according to the
to the(see
weaker equation:
H2Table
equation: 26.2).
(g) evolved H2(g) evolved H2(g) evolved
rboxylate anion, the O NaOH(aq) no reaction O dissolves O–
dissolves
sing the stability of
R C
Na2CO3(aq) H+ +
no reaction
R C
no reaction C
CO2(g)
R
evolved

–
O H Atoms or groups that draw electronsOaway from the ¬CO − groupOwill help the anion
2
to form, and this causes the acid to be more dissociated (that is, to become a stronger
They are moreacid).
acidic
Onthan alcohols
the other because
hand, groups that the negative
donate electronscharge on the
to the ¬CO −
2 group will
The stronger an acid the more it dissociates in aqueous
cause the acid to become weaker (see Table 26.2).or solution (position
anion can be delocalised
of equilibrium overtotwo
lies more theelectronegative oxygen
right). Acid strength atoms. described
is sometimes
e 26.1 In the carboxylate anion, the OO( 2 –) O–
1
O
e is spread, increasing the stability using
of the pKa value. The lower the pKa value the stronger the acid. pKa is
n. R C H+ + RR CC C R
a log scale and therefore a change in pKa of one unit indicates a ten-fold
OO–( 2 –)
1
O H O

1
Electron-donating groups decrease the acid strength of carboxylic acids, whereas electron-
withdrawing groups increase their acid strength.
or

y of some carboxylic 26_01 Cam/Chem AS&A2 Percentage dissociation in O( 2 –)

1
Formula of acid pKa
Topic 22 that
1.0 mol dm−3 aqueous solution
[H+ (aq)][A − (aq)] Barking Dog Art R C
Ka = O
[HA(aq)]
O ( 2 –)
1
he dissociation H C 3.75 1.3%
OH Electron-donating groups decrease the acid strength of carboxylic acids, whereas electron-
O withdrawing groups increase their acid strength.
ACIDITY
CH3 C 4.76 0.42%
26.2 The acidity of some carboxylic 26_01 Cam/Chem AS&A2
Formula of acid pKa Percentage dissociation in
Remember from Topic 22The that increasing
OH acidities of alcohols, phenols and carboxylic acids aredmexplained

−3
1.0 mol aqueous solution
+ −
[H (aq)][A (aq)] Barking Dog Art
−log10 Ka, where Ka = by O
the increasing abilityOof the molecular structures to delocalise the negative
[HA(aq)]
CH 3CH2
ds undergoing the dissociation C H C phenoxide4.87 0.36%
3.75 anions. 1.3%
H+ + A−.
charge in the alkoxide, and carboxylate
OH OH
Carboxylic acids – derivatives and further reactions
Their relative acidities
O areO demonstrated by their different reactions with
sodium,
Cl CHsodium
2 hydroxide
C CH 3 C and sodium
2.87 carbonate.
4.76 3.7% 0.42%
NaOH and Na2CO3 OH
Reagent OH Observation with
ties of alcohols,
Cl O HexanolO Phenol Hexanoic acid
CH C CH 3CHH2 (g) Cevolved 1.26 4.87 21%
Na(s) 2 H2(g) evolved H2(g)0.36%
evolved
Cl OH OH
NaOH(aq) no reaction dissolves dissolves
Cl O O
Na2CO3(aq) no reaction no reaction CO2(g) evolved
Cl C C Cl CH2 C 0.66 2.87 59% 3.7%
Cl OH 2
OH away from the ¬CO2 group will help the anion −
Atoms or groups that draw electrons
to form, and this causes
Cl the acid
O to be more dissociated (that is, to become a stronger
Worked example −
acid). On the other hand,
CH groups
C 1.26 to the ¬CO2 21%
that donate electrons group will
cause
The the
pKa acid to become
of fluoroethanoic
Cl
weaker
acid (see Table 26.2).
is 2.57.
OH
a Does this mean it is a stronger or a weaker acid than chloroethanoic acid? Explain
ylate anion, the O answer. Cl
your O O O–
the stability of
CEDAR COLLEGE
bC What pKa would
Cl you C expect
C forHdifl
+ uoroethanoic ACYL CHLORIDES & ACIDS
R + R Cacid?
0.66 59% C R
Cl OH 441
O H O– O
H+ ion is attracted back
d the acid is weaker.
than ethanoic acid 116
e I atom. Carboxylic acids – derivatives and further reactions

H and Na2CO3
RELATIVE ACIDITIES
The greater acidity of
Reagent Observation with
of alcohols, chloroethanoic acid—is sometimes
Atoms or groups that draw electrons away from
Hexanol the —CO2 groupHexanoic
Phenol will help the
acidanion
explained in terms of the stability
will be a stronger to
acidform, and this causesHthe acid to be more dissociated
Na(s) 2(g) evolved H2acid.
of the The Cl(that
(g) evolved atomis,istoHbecome a stronger
2(g) evolved
n/conjugate base formed
acid), e.g. halogens.
NaOH(aq) no reaction electron-withdrawing
dissolves and pullsdissolves
asing group the acid will The difference in acidity can b
electron density from the COOH
bilisation of the anion/
Na
On the CO (aq)
2 other no reaction
hand, groups that donate electrons no reaction
tomakes
the —CO CO
group (g) evolved of the anion (conjugate base) fo
the 2 will cause the
3 —
group. This the H
2 of
atom and, in the chloroethanoa
acid to become weaker, e.g. alkyl groups.COOH group more −positive and
the or groups that draw electrons away from the ¬CO2 group will help the the
lectron density onAtoms COO− group (Figure G28
anion
thus more likely to be lost as a
us be attracted back
tomore
form, and this causes
Electron-donating groupsthe acid to the
decrease be more
acid dissociated
strength (that is, toacids,
of carboxylic become it attracts the H+ ion back less
a stronger
whereas
proton.
e and the acid weaker.
acid). Onwithdrawing
electron- the other hand, groups
groups that donate
increase electrons
their acid to the ¬CO2− group willmore stable. A more stable conj
strength.
cause the acid to become weaker (see Table 26.2). dissociate and, therefore a stron

anion, the
ached to the O O O–
stability of The total negative charge in
tron density onRthe C H+ + R C C more
R over the whole anion
ck more strongly (Figure being localised on the COO
able for ethanoic acid O H O– O
3

or

O( 2 –)
1

R C

O ( 2 –)
1

Electron-donating groups decrease the acidAnstrength of carboxylic acids,

electron-withdrawing effectwhereas electron-
Again, we will consider the
RELATIVE ACIDITIES
withdrawing groups increase their acid strength.
is sometimes called a negative formed. Three very electronega
inductive effect. withdrawing effect than just on
carboxylic 26_01 Cam/Chem AS&A2 −
Formula of acid pKa Percentage dissociation in away from the COO group m
that
is often
− called aBarking Dog Art 1.0 mol dm−3 aqueous solution
aq)][A (aq)]
HA(aq)] O
ation H C 3.75 1.3%
OH
O
CH3 C 4.76 0.42%
OH
O
CH 3CH2 C 4.87 0.36%
OH
O 4

Cl CH2 C 2.87 3.7%

OH
Cl O
CH C 1.26 21%
Cl OH
CEDAR COLLEGE ACYL CHLORIDES & ACIDS
Cl O
Cl C C 0.66 59%
 [HA(aq)] O
dissociation H C 3.75 1.3% O( 2 –)
1

OH 117
R C
O
O ( 2 –)
1

CH3 C 4.76 0.42%

Electron-donating
OH groups decrease the acid strength of carboxylic acids, whereas electron-
RELATIVE ACIDITIES
withdrawing groups increase their acid strength.
O
f some carboxylic CH 3Cam/Chem
26_01 CH2 C AS&A2 4.87 0.36%
Formula of acid pKa Percentage dissociation in
pic 22 that OH 1.0 mol dm−3 aqueous solution
[H+ (aq)][A − (aq)] Barking Dog Art
= O O
[HA(aq)]
dissociation Cl CCH2
H C 2.87
3.75 3.7%
1.3%
OH OH
Cl O O
CH3 CH C C change
1.26in acid strength. The
4.76 21%pKa value for methanoic acid is approximately
0.42%
Cl
one less than that for ethanoic acid and, therefore, methanoic acid is
OHOH
roughly ten times stronger than ethanoic acid (Table G2).
Cl OO
Cl 3CH
CH C 2 CC 0.66carboxylate ion actually
4.87 59%
0.36%has both C–O distances equal and
The
change in acid strength.
Cl The pKOH value for methanoic acid
a OH is approximately
between the length of a C–O single bond and a C=O double bond.
one less than that for ethanoic acid and, therefore, methanoic acid is better described by the delocalised structure:
It is, therefore,
O
roughly ten times Worked
stronger than ethanoic acid (Table G2).
example
5

Cl CH2 C 2.87 3.7%

The pK of fluoroethanoic acid is 2.57.
The carboxylate ion aactually hasOH both C–O distances equal and
a Does this mean it is a stronger or a weaker acid than chloroethanoic acid? Explain
between the lengthCl of a C–O O single bond and a C=O double bond.
your answer.
It is, therefore, better described
CH pKC by the delocalised structure:
1.26
b What a would you expect for difluoroethanoic acid? 21%
Cl OH 441
Cl O The dissociation of ethanoic acid and chlorethanoic acid may be shown as:
Cl C C 0.66 59%
CHLOROETHANOIC
Cl OH ACID VS ETHANOIC ACID 07/11/14 2:06 PM

Chloroethanoic acid is a stronger acid than ethanoic acid.

The dissociation ofWorked
ethanoic example
acid and chlorethanoic acid may be shown as:
The pKa of fluoroethanoic acid is 2.57.
a Does this mean it is a stronger or a weaker acid than chloroethanoic acid? Explain
The greateryour
acidity of
answer.
chloroethanoic
b Whatacid
pKaiswould
sometimes
you expect for difluoroethanoic acid?
explained in terms of the stability
441
of the acid. The Cl atom is
electron-withdrawing and pulls
electronThe difference
density in acidity can The
from the COOH
difference in acidity can be explained by considering the stability
be explained by considering the stability of
of the anion (conjugate base) formed. The Cl is a very electronegative
group. This makes the H of the
the anion (conjugate base) formed.
COOH group more positive and
atom and, in the chloroethanoate ion, pulls electron density away2:06
07/11/14 fromPM
−
the COO group (Figure G28). Since the COO group is less negative,
thus more likely to be lost as a
The more stable the anion (conjugate H+ ionis,
it attracts thebase) more
back likely isThe
less strongly. itsconjugate
formation.
base is, therefore,
proton.
more stable.
The difference in acidity can be explained by considering A more stable conjugate base indicates a greater tendency to
the stability
dissociate and,
of the anion (conjugate base) formed. The Cl is a very electronegative
6 therefore a stronger acid.
atom and, in the chloroethanoate ion, pulls electron density away from
the COO− group (Figure G28). Since the COO groupThe is less negative,
total negative charge in the anion is still 1− but it is spread out
it attracts the H+ ion back less strongly. The conjugate base is, therefore,
more over the whole anion in the chloroethanoate ion rather than
more stable. A more stable conjugate base indicates a greater
beingtendency
localised to
on the COO− group.
dissociate and, therefore a stronger acid.
CEDAR COLLEGE ACYL CHLORIDES & ACIDS
The total negative charge in the anion is still 1− but it is spread out
more over the whole anion in the chloroethanoate ion rather than
 The carboxylate ion actually has both C–O distances equal and
between the length of a C–O single bond and a C=O double bond.
It is, therefore, better described by the delocalised structure:
118

The greater acidity of

chloroethanoic acid is sometimes
CHLOROETHANOIC ACID explained in terms of the stability
VS ETHANOIC ACID
of the acid. The Cl atom is
The Cl is a very electronegative atom and, in the chloroethanoate ion,
electron-withdrawing andpulls
pulls
The dissociation of ethanoic acid and chlorethanoic acid may be shown as: The differenc
electron density away from the CO2— group. electron density from the COOH
of the anion (
group. This makes the H of the
Since the COO group is less negative, it attracts the H+ ion back less strongly. atom and, in t
COOH group more positive and
the COO− gr
The conjugate base is, therefore, more stable.thus more likely to be lost as a it attracts the
proton.
A more stable conjugate base indicates a greater tendency to dissociate and, more stable. A
therefore a stronger acid. dissociate and

The total n
more over
The difference in acidity can be explained by considering the stability being local
of the anion (conjugate base) formed. The Cl is a very electronegative
atom and, in the chloroethanoate ion, pulls electron density7 away from
the COO− group (Figure G28). Since the COO group is less negative,
it attracts the H+ ion back less strongly. The conjugate base is, therefore,
more stable. A more stable conjugate base indicates a greater tendency to
dissociate and, therefore a stronger acid.

The total negative charge in the anion is still 1− but it is spread out
more over the whole anion in the chloroethanoate ion rather than
being localised on the COO− group.
TRICHLOROETHANOIC ACID VS CHLOROETHANOIC ACID Again, we w
An electron-withdrawing effect
is sometimes called a negative formed. Three
Trichloroethanoic acid is a stronger acid than chloroethanoic acid.
inductive effect. withdrawing
+
to attract back the H (Figure G29). The trichloroethanoate ion away from the
is thus relatively more stable than the chloroethanoate ion and so
trichloroethanoic acid dissociates more.

Again, we will consider the stability of the anion/conjugate base

Threevery
formed. Three very electronegative
electronegative Cl atoms
Cl atoms have electron-
have a greater a greater electron-withdrawing effect
withdrawing
thaneffjust
ect than
one.just one.electron
More More electron density
density is thus
is thus pulledaway from the COO− group
pulled
away from the COO− group making it less negative and less likely
making it less negative and less likely to attract back the H+.
Iodine is a less electronegative atom than chlorine and thus withdraws
The trichloroethanoate ion is thus relatively more stable than the chloroethanoate
less electron density from the COO− group. The COO group is thus
ion and
more negative so trichloroethanoic
in the iodoethanoate ion andacid
the Hdissociates
+ more.
ion is attracted back
more strongly. The conjugate base is less stable and the acid8 is weaker.
Iodoethanoic acid is, however, still a stronger acid than ethanoic acid
because of the electron-withdrawing nature of the I atom.
In general, for compounds of the form:

CEDAR COLLEGE ACYL CHLORIDES & ACIDS

if X is an electron-withdrawing group, the acid will be a stronger acid
than ethanoic acid due to stabilisation of the anion/conjugate base formed
 withdrawing group. The dissociation constantsH of O Cl acid
weakest
gative charge on the COO− group of the O
ethanoic acid−and its three substituted chloro derivatives (Ka = 1.7 × 10–5 mol dm–3)
ylate ion, stabilising the COO group and H C C H C C
are shown in Table 25.1. 119
g it less likely to bond with an H+ ion. O H
H H O H
e atoms are an example of an electron-
er delocalise
wing
− group. The dissociation constants H of weakest Cl acid Cl
group of the Acid O O/
(Ka = at
K 1.7 25× 10°C–5 O
c acid− and its three substituted chloro derivatives a mol dm–3)
OO group and MULTIPLE H C CCHLORINE H mol C dmC
SUBSTITUTES
−3
Cl ON C ACIDS
C
wn in+Table 25.1.
an H ion. ethanoic acid, CH −5
H 3COOH O H 1.7 ×10 O H
H H O H
n electron- −3
chloroethanoic acid, CH2ClCOOH 1.3 ×10
n constants of Cl Cl −2 Cl
ed chloro derivatives dichloroethanoic K a at
acid, 25 °C
O / COOH
CHCl 2 5.0 × 10 O O
−3
trichloroethanoic H mol Cacid,dmC CCl3COOH Cl 2.3 C × C −1
10 Cl C C strongest ac
−5 (Ka = 2.3 × 1
ic acid, CH3COOH 1.7 ×10O H O H O H
Table 25.1 The larger H the value of Ka, the stronger the acid.H Cl
thanoic acid, CH2ClCOOH 1.3 ×10−3
Cl Cl
oethanoic Ka at 25 °C
acid, CHCl/ 2COOH CH2ClCOOH 5.0 ×10O−2 CHCl2COOH O CCl3COOH this H is lost most
molacid, −3
dm CCl Trichloroethanoic Cl acid,
C2.3 CCl3COOH, hasClthree
C10 −1 strongly
C1.29 C strongest acid and the CCl3COO –
oethanoic 3COOHpKa 2.87 × 0.65 –1
(Ka = 2.3 × 10 mol dm–3) formed is least attr
1.7 ×10−5 electronegative Cl atoms all O
withdrawing
H
electrons from O H to H+ ions
1 The larger the value ofthe Ka, theCOOH
stronger the H
acid.
group, weakening the O H bond more Cl
H 1.3 ×10−3
than the other acidsCl in Table 25.1. Once the O H Figure
OH 5.0 ×10−2 bond is broken, the resulting O this H is25.2
lost The
mostmore
easilyelectron-withdrawing groups o
anion is also stabilised COOH group, the
– stronger the acid.
oethanoic2.3 acid,×10CCl
−1 3COOH, has Cl three strongly strongest acid and the CCl3COO ion
H more effectively byC its threeC
electron-withdrawing Cl –1
(Ka = 2.3 × 10 mol dm ) –3 formed is least attractive
egative Cl atoms all withdrawing electrons from Hto H+ ions. This makes
nger the acid. atoms, making it less Cl attractive
O to H+ ions
OOH group, weakening the O H bond more
the CCl3COOH the strongest of the acids listed in
9
Check-up
other acids in Table 25.1. Once the O H Figure
Table 25.1 as it has most Cl atoms (Figure this H is25.2
25.2). The more
lost most easilyelectron-withdrawing groups on the C atom in the
broken, the resulting anion is also stabilised COOH group,
and the CCl3COO – ion the stronger the acid. 1 a Place the following acids in orde
H, has three strongly
ectively by its three electron-withdrawing Cl formed is least attractive starting with the strongest acid
wing electrons from + +
making it less attractive to H ions. This makes to H ions CH3CH2COOH CH3CCl2C
O H bond more Check-up
3COOH the strongestFact of thefiacidsle listed in CH3CHClCOOH
Once the O H Figure 25.2 The more electron-withdrawing groups on the C atom in the
5.1 as it has most Cl atoms (Figure 25.2).
is also stabilised Trichloroethanoic
to COOH
attract acid
group,
back is
theused Hfor
stronger
the + chemical 1 The
facial
the acid.G29).
(Figure a Place
peels in the followingion
trichloroethanoate acidsbin Explain
order of why ethanoic acid is a
strength,
-withdrawing Cl clinics. It isis thus
used relatively
as a ‘medium’ more strength
stable peel
thantothe remove deep withion
starting
chloroethanoate theand strongest
so acid
acidthan
first.ethanol.
+
ions. This makes wrinkles and imperfections on
CHLOROETHANOIC
trichloroethanoic thedissociates
acid skin. The immediate
ACID more. CH VS results
3CH IODOETHANOIC
2COOH CH Predict
c 3CCl 2COOH
which would be the str
ACID
efiacids make the Check-up
face look like it has severe sunburn and patients are acid – methanoic acid or ethan
le listed in usually kept in hospital for a week.
CH3CHClCOOH
Figure 25.2). Chloroethanoic acid isfollowing
a stronger acidExplainthanofiodoethanoic and explain your reasoning.
roethanoic acid is used for chemical facial1 apeels Placein the acids bin order why ethanoic acid.
strength, acid is a stronger
It is used as a ‘medium’ strength peel to remove deep with the strongest acid than
starting first. ethanol.
es and imperfections on the skin. The immediate results Predict which would be the stronger
CH3CH2COOH CHc3CCl COOH 25.2 Acyl chlorides
he face look like it has Ethanoic
severe sunburn acidand is the
patientsweakestare acid in Table 25.1,acid as2 the – methanoic acid or ethanoic acid –
CH3CHClCOOH
methyl group is electron
y kept in hospital for a week. donating. This has theand opposite
explain yourMany useful compounds can be synthesise
reasoning.
cal facial peels in effIodine b
ect to electron-withdrawing Explain why ethanoic
groups: acid is a stronger carboxylic less acids. However, the synthetic re
peel to remove deep is aIodine
less electronegative
is a less
acid electronegative
than ethanol. atom than atom chlorine
than chlorine and andthusthus
withdraws
withdraws electron
• it strengthens the Odensity H bond in theCOO acid’s− group. The COO group are isneeded
thus can be difficult to do because c
The immediate results density less from electron
the
c CO2— group.
Predict from the
which would be the stronger
cburn
acidandis patients
the weakest
COOH
are acid in Table
• itThe
donates
more group negative
25.1, acidas the – methanoic 25.2 Acyl chlorides
in the iodoethanoate ion and
acid or ethanoic
− acid –
acids areback
the H+ ion is attracted quite unreactive. One way round
COOnegative group ischarge thusThemore towards the
negativebase isCOOinless
thestable group
iodoethanoate
and the acid ion convert
and the the carboxylic
H+ ion is acid into a compou
group is electron donating. Thmore is hasstrongly.
theand opposite
explain
conjugate
your Many
reasoning. useful compounds canis weaker.
be synthesised from
of the carboxylate
Iodoethanoic ion,acid making it more
is, however, stilllikely
a strongertobase
accept
acid than
less ethanoicacyl acid
chloride. Acyl chlorides are much mo
electron-withdrawingattracted groups:
+
back more strongly. The conjugate
carboxylic acids. is However, stabletheand the acid
synthetic is weaker.
reactions that
an H ion. because of the electron-withdrawing nature of the I atom. than carboxylic acids.
ngthens the O H bond in the acid’s stillare needed
Iodoethanoic acid is,for
In general, however,
compounds a stronger
of the form:can acidbethan diffiethanoic
cult to doacid because
becausecarboxylic
of the
OH group 25.2 Acyl chlorides
Table 25.1, as the electron-withdrawing nature of the I atom.
ates negative charge towards the COO− group
acids are quite unreactive. One way round this is to first
25 Carboxylic acids and acy
This has the opposite convert the carboxylic acid into a compound called an
carboxylate ion, making it more Many useful
likely compounds can be synthesised
to accept
10 from
ps: acyl chloride. Acyl chlorides are much more reactive
ion. carboxylic acids. However, the synthetic reactions that
he acid’s than carboxylic acids.
are needed can be difficult to do because carboxylic
if X isare
acids anquite
electron-withdrawing
unreactive. Onegroup, way round the acid willis be
this to afistronger
rst acid
than ethanoic acid due to stabilisation of the anion/conjugate 25 Carboxylic acids and acyl compounds 385
the carboxylic acid into a compound called an base formed
−
the COO group convert
when the acid dissociates. If X is an electron-releasing group the acid will
more likely to accept acyl chloride. Acyl chlorides are much more reactive
CEDAR COLLEGE be a weaker acid than ethanoic acid due to destabilisation of theACYL anion/CHLORIDES & ACIDS
than
conjugatecarboxylic acids.
base formed.
An electron-releasing group will increase the electron density on the
+
 120

HALOGENOCARBOXYLIC ACIDS

to attract back the H+ (Figure G29). The trichloroethanoate ion

is thus relatively more stable than the chloroethanoate ion and so
trichloroethanoic acid
CH2BrCOOH CHdissociates
2ClCOOH
more. CH2FCOOH
pKa 2.9 2.86 2.66

11

Iodine is a less electronegative atom than chlorine and thus withdraws

less electron density from the COO− group. The COO group is thus
more negative in the iodoethanoate ion and the H+ ion is attracted back
more strongly. The conjugate base is less stable and the acid is weaker.
Iodoethanoic acid is, however, still a stronger acid than ethanoic acid
because of the electron-withdrawing nature of the I atom.
EFFECT OF SUBSTITUENTS
In general, ON ACIDITY
for compounds of the form:

In general, for compounds of the form:

if X is an electron-withdrawing group, the acid will be a stronger acid

if X is an electron-withdrawing group, the acid will be a stronger acid than ethanoic
than ethanoic acid due to stabilisation of the anion/conjugate base formed
acid due to stabilisation of the anion/conjugate base formed when the acid
when the acid dissociates. If X is an electron-releasing group the acid will
dissociates.
be a weaker acid than ethanoic acid due to destabilisation of the anion/
conjugate base
If X is an electron-releasing groupformed.
the acid will be a weaker acid than ethanoic acid
due to the increaseAn theelectron-releasing
electron density on group
the COO will increase
group in thethe electron
anion and thedensity
H+ ion on the
COOback
will thus be attracted group
moreinstrongly.
the anionTheand the H+base
conjugate ioniswill thus be
therefore lessattracted
stable back more
strongly. The conjugate base is therefore less stable and the acid weaker.
and the acid weaker.
12

Ethanoic acid has an electron-releasing group attached to the

COO−group in the anion. This increases the electron density on the
COO group and therefore the H+ is attracted back more strongly (Figure
CEDAR COLLEGE G30). This means that the conjugate base is ACYL
less stable for ethanoic
CHLORIDES acid
& ACIDS
and, it is, therefore a weaker acid.
 conjugate base formed. Ethanoic acid has an electron-releasing group attached to the
less electron density
An from the COO− group.
electron-releasing groupThe will COO group
increase the
COO
is thus
−
electron density
group in theonanion.
the This increases the electron density on the
+
more negative COO
in the group
iodoethanoate ion and the H + ion is attracted back
in the anion and the H ion will COO thus begroup
attracted
and back morethe H+ is attracted back more strongly (Figure
therefore
more strongly. The conjugate base is less 121
strongly. The conjugate basestable and theless
is therefore acid is weaker.
stable
G30). and themeans
This acid weaker.
that the conjugate base is less stable for ethanoic acid
Iodoethanoic acid is, however, still a stronger acid than ethanoic acid
and, it is, therefore a weaker acid.
because of the electron-withdrawing nature of the I atom.
In general, for compounds
Ethanoic of an
acid has theelectron-releasing
form: group attached to the
COO−group in the anion. This increases the electron density on the
ETHANOIC ACID VS METHANOIC ACID
COO group and therefore the H+ is attracted back more strongly (Figure
G30). This means
Ethanoic acid isthat the conjugate
a weaker base ismethanoic
acid than less stable for ethanoic acid
acid.
and, it is, therefore a weaker acid.
if X is an electron-withdrawing group, the acid will be a stronger acid
than ethanoic acid due to stabilisation of the anion/conjugate base formed
when the acid dissociates. If X is an electron-releasing group the acid will
be a weaker acid than ethanoic acid due to destabilisation of the anion/
conjugate base formed.
Ethanoicgroup
An electron-releasing acid has an electron-releasing
will increase group
the electron density on attached
the to the CO2— group in the anion.
The electron-releasing effect of an alkyl group is often called a
COO group in the anion and the H+ ion will thus be attracted back more
This increases the electron density on acidpositive
the COO inductive eff ect.
group and therefore the H+ is attracted
strongly. The conjugate base is therefore less stable and the weaker.
back more strongly.

Ethanoic acid has an means

This electron-releasing group attached
that the conjugate basetoisthe
less stable for
−
COO group inethanoic
the
Theanion. This increases
electron-releasing
acid and, the
effectelectron
of an density
alkyl group
it is, therefore a weaker onisacid.
the
often called a
COO group and positive the H+ is
thereforeinductive attracted
effect. back more strongly (Figure
G30). This means that the conjugate base is less stable for ethanoic acid
13
and, it is, therefore a weaker acid.

LARGER CARBOXYLIC ACIDS

Beyond an ethyl group, the size of the alkyl group makes little difference to the
The electron-releasing effect of an alkyl group is often called a
electron-releasing
positive inductive effect. effect.

Thus propanoic acid is slightly stronger than ethanoic acid (the electron-
releasing effect of an ethyl group is slightly greater than that of a methyl group)
but propanoic acid, butanoic acid and pentanoic acid all have very similar acid
strengths.
HCOOH CH3COOH C2H5COOH C6H5COOH
pKa 3.77 4.76 4.88 4.2

14

CEDAR COLLEGE ACYL CHLORIDES & ACIDS

 Beyond an ethyl group, the size of122the alkyl group makes little
difference to the electron-releasing effect. Thus propanoic acid is slightly
id, butanoic acid stronger than ethanoic acid (the electron-releasing effect of an ethyl
c acid all have very
group is slightly greater than that of a methyl group) but propanoic acid,
trengths because of the
butanoic acid and pentanoic acid all have very similar acid strengths.
EFFECT OF DISTANCE OF Cl ATOMS ON ACIDITY
y which alkyl groups
ons. This arises because
p of electron density in
her C–H or C–C) with
2-Chlorobutanoic acid is a stronger acid than 4-chlorobutanoic acid.
n an adjacent atom – 2-Chlorobutanoic acid is a stronger acid than 4-chlorobutanoic acid.
n/hyperconjugation. The further the Clfurther
The is from
thethe
Cl isCO
from group
2— the COOin − the anion, the smaller the electron-
group in the anion, the smaller
the electron-withdrawing
withdrawing effect it has on it. eff ect it has on it.

15

s with blue litmus and

ith sodium hydroxide.
ever a weaker The dissociation of phenol may be shown as:
arboxylic acids. C6H5OH C6H5O− + H+
be distinguished from
ids by the fact that it or, showing structures:
rate CO2 from sodium
bonate solutions, i.e. it
cid than carbonic acid.
BENZOIC ACID
ore soluble in sodium
In benzoic acid, C6H5COOH, the pi orbital of the carbonyl group is in
lution than in water. It
he sodium hydroxidethe same plane as the of
The dissociation piethanol
orbitals
is: of the ring and hence the acid
− +
onic salt (C6H5O group
Na ) is able to interact and attract electrons from the ring forming
e there are stronger
a more stable anion.
with water molecules.

Again 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 (Figure G31). This spreads out the negative
charge in the ion. The O is thus less negative and the H+ is not attracted
back as strongly. The anion is thus stabilised and phenol is a stronger acid
than ethanol. In ethanol this delocalisation does not occur and indeed the
negative charge on the O in the ethoxide
16 ion is increased by the electron-
donating alkyl group.

CEDAR COLLEGE ACYL CHLORIDES & ACIDS

 acid. This is due to the greater electron-withdrawing ability of the highly electronegative
fluorine atom.
CO2H b Difluoroethanoic acid would be expected to have a lower pKa than dichloroethanoic acid
123
ning. – about 1.0.
values of
d (pKa = 2.86) and
d (pKa = 4.53) The effect of electron-donating or electron-withdrawing groups is seen even when
ct the pKa value such groups are situated RELATIVE of a benzene ring to the ¬CO2H group
ACIDITIES
on the opposite side
acid. (see Table 26.3).

Formula of acid pKa Percentage dissociation in

1.0 mol dm-3 aqueous solution
4.20 0.80%
CO2 H

4.37 0.73%
CH3 CO2H

n pKa for benzoic acid 3.99 1.0%

electron-withdrawing Cl CO2H

26.2 The further oxidation of some

carboxylic acids 17

Unlike other aliphatic carboxylic acids, methanoic acid does not contain an alkyl
chain attached to the ¬ CO2H group. Instead, the H¬ CO group, consisting of a
hydrogen atom attached to a carbonyl group, has some reactions in common with
aldehydes. In particular, it undergoes oxidation with common oxidants such as
acidified dichromate(VI).
3H¬CO2H + Cr2O72−(aq) + 8H+(aq) → 2Cr3+(aq) + 3CO2(g) + 7H2O(l)
It also reacts with both Fehling’s solution and Tollens’ reagent (see page 301).
SKILL CHECK 1
H¬CO2H(aq) + 2Cu2+(aq) + 6OH–(aq) → CO32−(aq) + Cu2O(s) + 4H2O(l)
Arrange theacid
Ethanedoic following intwo
contains order of acid
adjacent strength
carbonyl (weakest
groups. first): of two
The proximity
δ+ carbon atoms weakens the C–C bond sufficiently for the molecule to be readily
phenol,
oxidised2-chloropropanoic acid, ethanol, 3-chloropropanoic acid,
by warm acidified manganate(VII).
propanoic acid, 2,2-dichloropropanoic
5HO2C¬CO – acid,
+ 2,2-difluoropropanoic
2+ acid,
2H(aq) + 2MnO4 (aq) + 6H (aq) → 10CO2(g) + 2Mn (aq) + 8H2O(l)
and
This2-methylphenol.
forms the basis of an accurate volumetric method of analysing solutions
containing ethanedioic acid or its salts.
In a similar type of reaction, `-ketoacids are oxidised by alkaline H2O2 with the
loss of a carbon atom.
R¬CO¬CO2H + H2O2 + 3OH– → R¬CO2– + CO32– + 3H2O

26.3 Acyl chlorides

In section 18.3 we saw how acyl chlorides can be prepared from carboxylic acids.
18
Most acid derivatives are prepared from carboxylic acids by the reactions described in
this topic. Figure 26.2 shows a chart summarising the interrelationships between the
various derivatives.

CEDAR COLLEGE ACYL CHLORIDES & ACIDS

 e The basic structure of an acyl chloride is:
h 124

Describe the reactions of acyl

chlorides with nucleophiles
Explain the mechanism for theACYL The basic structure of an acyl chloride is:
CHLORIDES
Acyl chlorides may be prepared by reacting carboxylic acids with
reaction of acyl chlorides with
TheSOCl or PCl5. of an acyl chloride is:
basic2 structure
nucleophiles
Describe the reactions of acid
anhydrides withnamed
They are nucleophiles
as alkanoyl chloride, e.g.
Acyl chlorides may be prepared by reacting carboxylic acid
SOCl2 or PCl5.

They are named as alkanoyl chloride, e.g.

These are extremely reactive and react to add an acyl group to

nucleophiles with the elimination of HCl.
19

These are extremely reactive and react to add an acyl grou

nucleophiles with the elimination of HCl.

1 Reaction with water

Acyl chlorides react violently with water to from carboxylic acids.
1 Reaction with water
FORMATION
Acyl chlorides react violently with water to from carboxyl
We can prepare acyl chlorides from their corresponding carboxylic acid
using phosphorus(V) chloride, phosphorus(III) chloride or sulfur
dichloride oxide (SOCl2)

20

CEDAR COLLEGE ACYL CHLORIDES & ACIDS

 125
These are extremely reactive and react to add an acyl group to
nucleophiles with the elimination of HCl.

REACTIVITY
The electronegativity of the oxygen, and the easily polarised C=O double bond, have a
dramatic effect on the reactivity
1 Reaction withofwater
acyl chlorides compared with that of chloroalkanes.
Acyl
Acyl chlorides react chlorides
readily react violently with water to from carboxylic acids.
with water:

we will meet the acyl group will be added to the

e atom of the nucleophile (N or O) and H (from
d Cl (from the acyl chloride) will be eliminated

hols
with alcohols to form esters. 21

This reaction is usually carried out

in the presence of a base such as
of phenol reacts with benzoyl chloride to form pyridine (C5H5N).

MISTRY
REACTIVITY
The electronegativity of the oxygen, and the easily polarised C=O double bond, have
Together
a dramatic effect with
on the what we
reactivity havechlorides
of acyl already seen in sections
compared 15.3
with that of and 25.4, we note that in
the reaction:
chloroalkanes.
monia
all the information given at + H O → R¬OH + HCl
25.4
R¬Cl
ammonia solution is added to an acyl chloride
and this sectionAcyl chlorides react readily 2 with water unlike halogenalkanes and halogenobenzene.
de is formed.
nation of why the the relative rates of hydrolysis are as follows:
s of these three chloro The relative rates of hydrolysis are as follows:
r in this way. Would you O
relative rates with NH3 or CH3 C > CH3CH2 Cl > Cl
gent, instead of H2O?
Cl
ay of writing this reaction would be as:

+ 2NH3 With
CH3CH2CONH2 + NH4Cl alcohols or phenols
formed in the presence of a base suchAcyl
as chlorides react readily with alcohols or phenols, forming esters:
r the salt ammonium chloride. O 22
O

nes
CH 3C ! HOCH 2 CH3 CH 3C ! HCl
s are reacted with amines (again at low Cl O CH 2 CH3
stituted amides are formed.

O O
CEDAR COLLEGE ACYL CHLORIDES & ACIDS
CH 3C ! HO
!base CH3C ! HCl
Cl O
 126

HYDROLYSIS WITH ALKALI

The hydrolysis of acyl chlorides is much faster with alkalis as OH— is a
stronger nucleophile than water.

23

26 Carboxylic acids – derivatives and further reactions

ADDITION ELIMINATION REACTION
26 Carboxylic acids – derivatives and further reactions
The carbonyl group in acyl chlorides can undergo
The mechanism nucleophilic
of the reactions addition in a similar
of acyl chlorides
The carbonyl group in acyl chlorides can undergo nucleophilic addition in a similar
manner to carbonyl compounds:
Themanner
mechanism
to carbonylof the reactions of acyl chlorides
compounds:

The carbonyl groupδ−in acyl chlorides can−

O undergo nucleophilic addition in a similar
•
•
manner to carbonylOcompounds:
δ+
R C R − C Cl
δ−
•
O Cl O •

− Nu
•
•

R δ+ Nu R C Cl
C
Unlike carbonyl
Cl compounds, however, acyl chlorides are provided with an easily
− Nu
•
•

Nu leaving group,
Unlike carbonyl compounds,removed
however, acylthechlorides
chloride ion:
are provided with an easily
Unlike carbonyl!compounds, however, acyl chlorides are provided with an easily
O
•
removed leaving group, the chloride ion:the chloride ion: O
•
removed leaving group,
R C Cl R C Cl!
O!
•
O Nu
•
Nu
R C Cl R C Cl!
Nucleophilic substitution has taken place, by a mechanism involving addition,
followed Nu
Nu by elimination.
If the nucleophile is water, the carboxylic acid is formed:
Nucleophilic substitution has taken place, by a mechanism involving addition,
O
followed by elimination. −
24 O
• −
O
• •
If theCH C O
•
nucleophile is water, the carboxylic acid is formed:
3
−H + −Cl
−
Cl CH3 C Cl CH3 C Cl CH3 C
O
•
•

O − −
O +O
•
O OH O OH
• •
CH3 C
•

H H −H + −Cl
−
•
•

Cl CH3 H
C ClH CH3 C Cl CH3 C
•
•

O + OH
O OH
HWorked
H example
•
•

H H
Draw the mechanism for the reaction between ammonia and benzoyl chloride:
CEDAR COLLEGE ACYL CHLORIDES & ACIDS
Worked example
COCl + 2NH3 CONH2 + NH 4Cl
Draw the mechanism for the reaction between ammonia and benzoyl chloride:
 127

ADDITION ELIMINATION REACTION

The mechanism of these reactions involves two steps:
The mechanism of these reactions involves two steps:
1. initial addition
1 initial of the
addition of nucleophile
the nucleophile
2 elimination
2. elimination of elements
of the the elements of HCl.
of HCl.
The basic mechanism can be illustrated by representing the nucleophile
X−: mechanism can be illustrated by representing the nucleophile as X—:
Theasbasic
–

The nucleophile attacks the + C of the C=O group. The π

component of the C=O breaks with 25the pair of electrons going to the
O to generate O−. A lone pair from the O then is used to re-form the
double bond and at the same time the C–Cl bond breaks.
Now, if we look at the reaction with water:
–
The mechanism of these reactions involves two steps:
1 initial addition of the nucleophile
+ 2 elimination of the elements of HCl.
The basic mechanism can be illustrated by representing the nucleophile
as X−ADDITION ELIMINATION REACTION
+
:
+
–

+
The second stage could also have been shown more simply as loss of a
proton (H+):

The nucleophile attacks the δ+ C of the C=O group.

The nucleophile attacks the + C of the C=O group. The π
The π component
component of ofthe
theC=O
C=O breaks
breaks with
with the the
pairpair of electrons
of electrons goinggoing
to thetoOthe
to
−
O to
generate O—generate
. O . A lone pair from the O then is used to re-form the
double bond and at the same time the C–Cl bond breaks.
A lone pair from the O then is used to re-form the double bond and at the same time
In Now, if we look
the second
the C–Cl bond breaks. stageatHthe
+ reaction with water:
is removed by interaction with a base. In the
– reaction of an alcohol with an acyl chloride the reaction is conducted
in the presence of a base. In the reaction with ammonia the proton is
+
removed by the ammonia/amine. 26
– +

+ +

+
–
CEDAR COLLEGE
+ The second stage could also have been shown more simply as loss of a
ACYL CHLORIDES & ACIDS
+
+ proton (H ):
 Cl
− Nu

•
•
Nu
Unlike carbonyl compounds, however, acyl 128
chlorides are provided with an easily
removed leaving group, the chloride ion:

O!
•
•
O
R ADDITION
C Cl ELIMINATION
R C Cl! REACTION
Nu
Nu
Nucleophilic substitution has taken place, by a mechanism involving
Nucleophilic substitution has taken place, by a mechanism involving addition,
addition, followed by elimination. If the nucleophile is water, the carboxylic
followed by elimination.
If the nucleophile is water, the carboxylic acid is formed:
acid is formed:
O −
•
O −
O
• •
CH3 C O
•

−H + −Cl
−
Cl CH3 C Cl CH3 C Cl CH3 C
•
•

O + OH
O OH
H H
•
•

H H

Worked example
Draw the mechanism for the reaction between ammonia and benzoyl chloride:

27
COCl + 2NH3 CONH2 + NH 4Cl

Answer
O O− O−

C C Cl C Cl

In all the reactions Cl

we will meet the acyl+group
N will be added to the N
NH3
most electronegative atom of the nucleophile
H (N NH
or O) and H (from
H H 3 H H
the nucleophile)−and Cl (from the acyl chloride) will be eliminated
O REACTION WITH ALCOHOLS +
(Figure G36 ). O NH4
−
Reaction
2 Acyl with Calcohols
chlorides Cl
react with alcohols to form C
esters.+ Cl

Acyl chlorides react

N
with alcohols to form esters.
NH2

H H

Now try this

Predict the products of, and suggest a mechanism for, the reaction between propan-1-ol This reaction is usually c
and propanoyl chloride.
in the presence of a base
An alkaline solution of phenol reacts with benzoyl chloride to form pyridine (C5H5N).
phenyl benzoate:
445

45 27/10/14 10:29 AM

28

3 Reactions with ammonia

When
CEDAR concentrated ammonia solution is added to an acyl chloride
COLLEGE ACYL atCHLORIDES & ACIDS
0 °C a primary amide is formed.
 most electronegative atom of the nucleophile (N or O) and H (from
the nucleophile) and Cl (from the acyl chloride) will be eliminated
(Figure G36 ). 129
2 Reaction with alcohols
Acyl chlorides react with alcohols to form esters.

REACTION WITH ALCOHOLS

An alkaline solution of phenol reacts with benzoyl chloride to form phenyl
benzoate.In all the reactions we will meet the acyl group will be added to the
Th
most electronegative atom of the nucleophile (N or O) and H (from
in
The phenol is
the An dissolved
nucleophile) in NaOH,
and Cl of
alkaline solution to the
(from make
phenol phenoxide
acyl chloride)
reacts which
will
with benzoyl is a stronger
bechloride
eliminated
to form pyr
(Figure
nucleophile, to G36
make ).the
phenyl benzoate:yield better.
2 Reaction with alcohols
Acyl chlorides react with alcohols to form esters.

This re
in the p
An alkaline solution of phenol reacts
29
with benzoyl chloride to form pyridin
3 Reactions with
phenyl benzoate: ammonia
When concentrated ammonia solution is added to an acyl chloride at
0 °C a primary amide is formed.

REACTION WITH AMMONIA

When 3concentrated
Reactions ammonia
A morewith waysolution
ammonia
accurate is added
of writing to an would
this reaction acyl chloride
be as: at 0°C
a primaryWhen
amideconcentrated
is formed. ammonia solution is added to an acyl chloride at
CH 3CH2amide
0 °C a primary COClis+formed.
2NH3 CH3CH2CONH2 + NH4Cl

HCl would not be formed in the presence of a base such as

ammonia but rather the salt ammonium chloride.

4 Reactions with amines

When acyl chlorides are reacted with amines (again at low
A more accurate N-substituted
temperature) way of writingamides are formed.
this reaction would be as:

CH3CH2COCl + 2NH3 CH3CH2CONH2 + NH4Cl

HCl would not be formed in the30 presence of a base such as

ammonia but rather the salt ammonium chloride.

4 Reactions with amines

Again,
When acylthe balanced
chlorides areequation should,
reacted with more(again
amines correctly,
at lowbe written as:
temperature) N-substituted amides are formed.
CEDAR COLLEGE ACYL CHLORIDES & ACIDS
CH3CH2COCl + 2CH3CH2NH2
CH3CH2CONHCH2CH3 + CH3CH2NH3Cl
 A more accurate way of writing this reaction would be as:
130
CH3CH2COCl + 2NH3 CH3CH2CONH2 + NH4Cl

HCl would not be formed in the presence of a base such as

ammonia but rather the salt ammonium chloride.
REACTION WITH AMINES
4 Reactions
When with amines
acyl chlorides are reacted with amines (at low temperature) N-
When acylamides
substituted chlorides
areareformed.
reacted with amines (again at low
temperature) N-substituted amides are formed.

Again, the balanced equation should, more correctly, be written as:

CH3CH2COCl + 2CH3CH2NH2
CH3CH2CONHCH2CH3 + CH
31
3CH2NH3Cl

CEDAR COLLEGE ACYL CHLORIDES & ACIDS