1

CARBOXYLIC ACID AND

ITS DERIVATIVES
2
C OH R
O
RCOOH or RCO
2
H
(R alkyl, aryl or H)
Structure
3
NOMENCLATURE
4
HCOOH
Methanoic acid
Formic acid
CH
3
COOH
Ethanoic acid
Acetic acid
CH
3
CH
2
COOH
ro!anoic acid
ro!ionic acid
CH
3
CH
2
CH
2
COOH
"#tanoic acid
"#tyric acid
CH
3
CH
2
CH
2
CH
2
COOH
entanoic acid
$aleric acid
IUPAC Nomenclature
Common Name
%
&
'he lon(e)t chain m#)t contain the car*o+yl (ro#!,
&
'he car!o"#l $rou% i) at the terminal, there-ore the car*on
o- the car*o+yl (ro#! i) not n#m*ered,
One COOH . car*o+yl (ro#! i) at one end
'/o COOH . car*o+yl (ro#!) are at *oth end)
&
0ame the com!o#nd a) alkane, &ro% 'e( )n al*ane an&
a&& 'o)c ac)&( (e(1 methano)c ac)&)
IUPAC Nomenclature
2
43*romo333methyl!entanoic acid
%3hydro+yhe+anoic acid
CH CH CH
2
CH CH
+
C O H
O CH
+
%3methyl333he+enoic acid
CH CH
2
CH C OH
O
CH
+
Br CH
+
CH
2
CH
2
CH
2
C OH
O
CH O H
CH
+
4
&
'/o COOH (ro#!), the com!o#nd /ill *e named a)
al*ane&)o)c ac)&5
(E+am!le1 ethanedioic acid, !ro!anedioic acid and etc)
CH
2
CH
2
CH
2
C OH
O
C O H
O
!entanedioic acid
6
C C
H
CH
2
H
CH
2
COOH
HOOC
tran) 33he+enedioic acid
CH
2
CH
2
CH C OH
O
CH
2
C O H
O CH
+
33methylhe+anedioic acid
7
&
8hen R i) an ar#l $rou%, the !arent name i) !en,o)c
ac)&
COOH Cl
43chloro*en9oic acid
1:
CH
CH
+
CH
+
HOOC
COOH
HOOC
COOH
1,33*en9enedicar*o+ylic acid
23i)o!ro!yl31,43*en9enedicar*o+ylic acid
&
An aromat)c &)car!o"#l)c ac)& )- name& a-
1,x-benzenedicarboxylic acid
11
&
A cyclic car*o+ylic acid i) named a) cycloalkanecarboxylic
acid
&
'he C atom /hich i) attached to ;COOH i) n#m*ered a)
C1
COOH
cyclo!entanecar*o+ylic acid
.
12
COOH
CH
+
Br
43*romo323methylcyclohe+anecar*o+ylic acid
.
COOH
cyclohe+anecar*o+ylic acid
.
13
COOH
COOH
COOH
COOH
Cl
1,23cyclohe+anedicar*o+ylic acid
43chloro31,23cyclohe+anedicar*o+ylic acid
A c#cl)c &)car!o"#l)c ac)& )- name& a-
1,x-cycloalkanedicarboxylic acid
14
COOH
CH
+
33methyl323cyclohe+enecar*o+ylic acid
&
8hen a com!o#nd contain) a car*o+yl (ro#! and other
-#nctional (ro#!()), the !riority i) (i<en to the car*o+ylic
acid a) the !arent name,
1%
PHYSICAL PROPERTIES O/
CARBOXYLIC ACIDS
12
Bo)l)n$ Po)nt
'he *oilin( !oint o- car*o+ylic acid i) hi(her than an alcohol, a
ketone or an aldehyde (/ith M
r
that almo)t the )ame) *eca#)e1
i, it e+i)t) a) )ta*le &)mer- that -orm hydro(en *ond,
ii, molec#le) in dimer) are arran(ed clo-el# %ac*e&,
there-ore the hydro(en *ond) are relati<ely )tron(,
iii, hi(h ener(y i) needed to o<ercome the intermolec#lar
-orce) ,
*oilin( !oint
14
C
O
O
R
H
C
O
O
R
H
H#&ro$en !on&
H#&ro$en !on&
16
C
O
O
R
H
O
H
H
C
O
O
R
H
O H
H
Solu!)l)t#
a0 Solu!)l)t# )n 1ater
&
Car*o+ylic acid) are )ol#*le in /ater d#e to the
-ormation o- 2#&ro$en !on& !et1een t2e 1ater
molecule- an& car!o"#l)c ac)& molecule-3
H#&ro$en Bon&-
17
&
T2e -olu!)l)t# o4 car!o"#l)c ac)& )n 1ater )- almo-t t2e -ame a- alco2ol3
&
Al)%2at)c car!o"#l)c ac)&- 1)t2 C 5 6 are )n-olu!le )n 1ater3 S),e o4 R 78
2#&ro%2o!)c area 73
R C OH
O
hydrophilic
hydrophobic
2:
&
Aromat)c car!o"#l)c ac)&- are -l)$2tl# -olu!le )n
1ater &ue to t2e 2u$e aromat)c r)n$3
&
D)car!o"#l)c ac)&- are relat)9el# more -olu!le -)nce
more 2#&ro$en !on&- are 4orme&3
21
E+am!le 1 =e)cendin( order o- )ol#*ility
CH CH
2
CH
2
CH
+
COOH COOH
CH
2
CH
2
CH
2
CH
+
COOH
CH
+
CH
2
CH
2
COOH
COOH
5
5
5
22
*, Solu!)l)t# )n non %olar -ol9ent
&
Car*o+ylic acid) are )ol#*le in non !olar )ol<ent )#ch a)
*en9ene d#e to the Van &er :aal- -orce) *et/een the
*en9ene and alkyl $rou% o4 car!o"#l)c ac)&- 3
C
O
O
R
H
C
O
O
R
H
Van &er :aal- 4orce- Van &er :aal- 4orce-
H#&ro$en !on&-
23
Ac)&)t# o4 Car!o"#l)c Ac)&
&
T2e ac)&)t# o4 car!o"#l)c ac)& )- )n4luence& !#;
)3 Re-onance e44ect
))3In&uct)9e e44ect
24

Car*o+ylate ion 1

heno+ide ion 1
R
C
O3
O
O3
Re-onance E44ect
2%
&
Car*o+ylic acid) are more acidic d#e to the re-onance
-ta!)l)-at)on o4 t2e car!o"#late )on,
&
'he electron) )n car!o"#late )on are delocali)ed
!et1een t1o o"#$en atom-8 /herea) )n %2eno")&e
)on, the electron) are delocali9ed )n t2e !en,ene r)n$3
&
'he C<O $rou% )n car!o"#l)c ac)& )- a electron=
1)t2&ra1)n$ $rou% /hich re&uce the electron den)ity
o- .OH, there-ore the .OH *ond *ecome) /eaker,
&
T2u- H
>
)- ea-)l# &onate& an& car*o+ylic acid i) more
acidic than !henol,
22
&
Car*o+ylic acid i) relat)9el# a 1ea* ac)&8 ho/e<er it i)
-tron$er t2an %2enol alco2ol
R
C
OH
O
>
OH
>
O H
2
> R
OH
24
OH O
=
>
H
+
O
>



phenoxide ion
(resonance structure)
> H
2
O
phenol
C R
O
OH
> H
2
O > H
+
O
>
carboxylate ion
(resonance structure)
C R
O
O
=
C R
O
=
O
carboxylic acid
R?O?H > H
2
O R?O
@
> H
+
O
>



alkoxide ion
alcohol
26
In&uct)9e E44ect
An electron /ithdra/in(
(ro#! (deacti<atin( (ro#!)
that attached to a
car*o+ylate ion /ill
delocali)e the ne(ati<e
char(e, there*y )ta*ili)e)
the car*o+ylate ion and
increa)e) acidity,
An electron donatin(
(ro#!, (acti<atin( (ro#!)
/ill de)ta*ili)e the
car*o+ylate ion and
decrea)e) acidity,
C E:A
O
O
=
C EDA
O
O
=
27
i. The inductive effect
electron-withdrawing group in the
copound
& electron3/ithdra/in( (ro#!)
Be3$ @NO
2
8=/8=Cl8=Br8 =I 0 red#ce the electron
den)ity o-
.O H,
& 'h#) the O=H !on& *ecome) 1ea*er and H
>
can
*e ea-)l# relea-e&,
& 'he com!o#nd i) )aid to *e more acidic
Electron= /ithdra/in( (ro#! )ncrea-e- the
ac)&)t#,
3:
& E"am%le;
CH
+
CHCl=COOH an& CH
+
CH
2
COOH
& Cl i) an electron=/ithdra/in( $rou%-8 there-ore re&uce t2e
electron &en-)t# o4 @OH3
& 'h#) the O=H !on& *ecome) 1ea*er and H
>
can *e ea-)l#
relea-e&,
& Ac)&)t# ;
.
CH
+
CHCl=COOH > CH
+
CH
2
COOH
& Electron=/ithdra/in( (ro#!) )ncrea-e the ac)&)t#,
31
&
E"am%le;
CH
+
CH/=COOH an& CH
+
CHCl=COOH
&
Bot2 / an& Cl are electron=attract)n$ $rou%3
&
'he electrone$at)9)t# o- / 5 Cl
& 'he electron &en-)t# o4 @OH in CH
+
CH/=COOH )- le--,
th#) the @OH !on& )- 1ea*er than in
CH
+
CHCl=COOH, 'here-ore, H
>
)- ea-)l# &onate&3
& Ac)&)t# ; CH
+
CH/=COOH 5 CH
+
CHCl=COOH
ii) The electronegativity of electron-
withdrawing group in the copound
32
&
E"am%le;
CH
+
CBCl0
2
=COOH an& CH
+
CHCl=COOH
& CH
+
CBCl0
2
=COOH conta)n- 2 Cl atom- that make the
*ond o- @OH 1ea*er than CH
3
CHCl3COOH (/ith onl#
one Cl atom), T2u-8 H
>
)- ea-)l# &onate&3
& Ac)&)t# ; CH
+
CBCl0
2
=COOH 5 CH
+
CHCl=COOH
iii) !uber of electron-attracting group in
the copound.
33
&
E"am%le;
CH
+
CH
2
CHBCl0COOH an& CH
2
BCl0CH
2
CH
2
COOH
&
'he &)-tance !et1een Cl atom an& car!o"#l $rou% )n
CH
+
CH
2
CHCl=COOH i) nearer com!are to in
CH
2
ClCH
2
CH
2
3COOH,
& 'he @OH !on& )n CH
+
CH
2
CHBCl0COOH i) 1ea*er t2an
in CH
2
ClCH
2
CH
2
3COOH, )o H
>
)- ea-)l# &onate&3
&
Ac)&)t# ;
CH
+
CH
2
CHBCl0COOH 5 CH
2
BCl0CH
2
CH
2
COOH
iv) The position of electron-attracting group
34
&
E"am%le;
CH
+
COOH an& CH
+
CH
2
COOH
&
=R i) an electron @relea-)n$ $rou%3
& 'he -),e o- .R (ro#! in CH
3
CH
2
COOH i) lar(er than in
CH
3
COOH, )o CH
3
CH
2
3 i) a -tron$er relea)in( (ro#!
than CH
3
3,
& 'he electron den)ity o- .OH in CH
+
CH
2
COOH
)ncrea-e- and H
>
)- &)44)cult to !e &onate&3

Electron=relea-)n$ $rou%- re&uce t2e ac)&)t# o4 a

car!o"#l)c ac)&3
(v ) The inductive effect of electron- releasing
(electron-donating) group in the copound
3%
SYNTHESIS O/
CARBOXYLIC ACIDS
32
C OH R
H
H
C O
R
H
C O
R
O H
oxidizing
agent
oxidizing
agent
1
o
alcohol aldehyde carboxylic acid
Common o+idi9in( a(ent) are ;
&CMnO
D
E H
2
SO
D
!ota))i#m !erman(anate
&C
2
Cr
2
O
F
G Na
2
Cr
2
O
F
EH
2
SO
D

!ota))i#m ?)odi#m dichromat ($@)
.3 O")&at)on o4 %r)mar# alco2ol an& al&e2#&e
34
23 O")&at)on o4 Al*#l Ben,ene
R
oxidizing
agent
COOH
CMnO
D
8 H
>
H
> CO
2
> H
2
O
COOH
Cl
CH
CH
+
CH
+
Cl
36
+3 /ormat)on an& H#&rol#-)- o4 n)tr)le
R CH
2
X
NaCN
R CH
2
CN
H
2
O8H
>
R CH
2
COOH
NaCN
H
2
O8H
>
CH
2
CN
CH
2
Br
CH
2
COOH
37
D3 Car!onat)on o4 Ar)$nar& Rea$ent-
R?M$X
O C O
CO
2
H
2
O8 H
>
R?COOH > M$BOH0X
CH
2
M$Br
H
2
O8 H
>
CH
2
COOH
> M$BOH0Br
4:
CHEMICAL PROPERTIES O/
CARBOXYLIC ACIDS
41
&
Main reaction) o- car*o+ylic acid,
a, 'he reaction that in<ol<e) the &onat)on o- H
>

-rom .OH (ro#!,
*, 'he reaction that in<ol<e) the -u!-t)tut)on o- OH
(ro#!
c, 'he reaction that in<ol<e) the red#ction /ith
AiAlH
4
to !rimary alcohol
42
a3 T2e react)on t2at )n9ol9e- t2e &onat)on o4
H
>
4rom @OH $rou%
.3 Neutral)-at)on
&
Car*o+ylic acid) are acidic, it can react /ith *a)e )#ch a)
0aOH (aB) to (i<e metal car*o+ylate )alt),
C R
O
OH
> NaOH
C R
O
O
=
Na
>
> H
2
O
43
> NaOH
> H
2
O
COOH
COO
@
Na
>
So&)um !en,oate
44
23 React)on 1)t2 electro%o-)t)9e metal- -uc2 a- Na8
C8 Ca8 M$ an& /e3
R C OH
O
C
R C O
O
M
C
H
2 M
E"erc)-e;
C
OH
O Cl
C
D
4%
!3 T2e react)on t2at )n9ol9e- t2e -u!-t)tut)on
o4 @OH $rou% Bto 4orm )t- &er)9at)9e-0
.3 Ac)& c2lor)&e 4ormat)on
Acid chloride can *e !re!ared -rom the reaction o-
car*o+ylic acid) /ith thionyl chloride, SOCl
2
E !ho)!horo#)
!entachloride, PCl
6
E !ho)!horo#) trichloride, PCl
+
R C OH
O
R C Cl
O
R C Cl
O
R C Cl
O
> SO
2
> HCl
> POCl
+
> HCl
> H
+
PO
+
SOCl
2
PCl
6
PCl
+
42
SOCl
2
PCl
6
PCl
+
CH C OH CH
+
CH
+
O
E+erci)e 1
44
> H?OR(
C OH R
O
C O R RI
O
> H
2
O
H
>
23 E-ter)4)cat)on
Car*o+ylic acid) react /ith alcohol) in the !re)ence o- mineral
acid cataly)t to !rod#ce e-ter-3
> HOCH
2
CH
+
H
>
CH
2
C CH
+
OCH
2
O
CH
+
CH
2
C CH
+
OH
O
> H
2
O
carboxylic acid alcohol ester
propanoic acid ethanol ethyl propanoate
46
+3 Ac)& an2#&r)&e 4ormat)on
Acid anhydride) can *e !re!ared -rom car*o+ylic acid) *y
the lo)) o- /ater thro#(h heatin(,
R C OH
O
R C O H
O
>
heat
CH
+
C O C CH
+
O O
R C O C R
O O
> H
2
O
CH
+
C OH
O
CH
+
C OH
O
>
heat
> H
2
O
ethanoic anhydride
acid anhydride
47
D3 Am)&e- 4ormat)on
Reaction o- car*o+ylic acid) /ith an
ammonia or amine (i<e amide,
R C OH
O
NH
+
RNH
2
R
2
NH
R C NH
2
O
R C NHR
O
R C NR
2
O
> H
2
O
> H
2
O
> H
2
O
1
o
aide
"
o
aide
(1
o
aine)
("
o
aine)
(#
o
aide)
%:
CH C Cl
O CH
+
CH
+
CH
+
NH
2
CH
+
NH
CH
+
NH
+
E+erci)e 1
%1
c3 T2e react)on t2at )n9ol9e- t2e re&uct)on 1)t2
L)AlH
D
to %r)mar# alco2ol
Car*o+ylic acid are red#ced to !rimary alcohol) *y
reaction /ith lithi#m al#mini#m hydride, AiAlH
4
,
C O R RI
O
L)AlH
D
et2er
CH
2
OH R
1
o
alcohol
> R(OH
C O CH
2
CH CH
+
CH
+
O
CH
+
L)AlH
D
et2er
CH
2
OH CH CH
+
CH
+
> HO?CH
2
CH
+
%2
Met2ano)c ac)&8 HCOOH a- a re&uc)n$ a$ent
&
Methanoic acid molec#le, ha) *oth
C OH H
O
C OH
O
and
&
@t )ho/) the !ro!ertie) o- *oth car*o+ylic acid and aldehyde,
&
@t al)o )ho/) red#cin( !ro!ertie) in reaction) /ith acidi-ied
DMnO
4
or D
2
Cr
2
O
4
and 'ollen)5 rea(ent,
C
O
H
car!o"#l)c
car!on#l
%3
C OH H
O
CMnO
D
E H
>
CO
2
> H
2
O > MnO
2
A$BNH
+
0
2
>
A$ > CO
2
> H
2
O
($rown)
%4
DERIVATIVES O/
CARBOXYLIC ACIDS
R C Cl
O
acid chloride
O C C R R
O
O
acid
anhydride
R C NH
2
O
aide
C O R RI
O
ester
%%
React)on- o4 car!o"#l)c ac)& &er)9at)9e-
)3 H#&rol#-)- o4 ac)& c2lor)&e-
R C Cl
O
H
2
O
R C OH
O
> HCl
acid chloride carboxylic acid
))3 H#&rol#-)- o4 ac)& an2#&r)&e-
O C C R R
O
O
H
2
O
carboxylic acid
2 C OH R
O
acid
anhydride
%2
React)on- o4 car!o"#l)c ac)& &er)9at)9e-
)))3 H#&rol#-)- o4 e-ter-
H
2
O
H
>
carboxylic acid
> ROH
H
2
O
NaOH
> ROH
alcohol
alcohol
Na
>
C O
=
R
O
C OR R
O
ester
R C OH
O
%4
React)on- o4 car!o"#l)c ac)& &er)9at)9e-
)))3 H#&rol#-)- o4 am)&e Bac)&)c 2#&rol#-)-0

R C NH
2
O
H
2
O
H>
R C OH
O
C
NH
D
>
aide
%arboxylic
acid
&oniu ion
%6
React)on- o4 car!o"#l)c ac)& &er)9at)9e-
)))3 H#&rol#-)- o4 am)&e Bal*al)ne 2#&rol#-)-0

R C NH
2
O
H
2
O
OH
=
C
NH
+
aide
aonia
R C O3
O
%arboxylate ion
%7
React)on- o4 car!o"#l)c ac)& &er)9at)9e-
)))3 H#&rol#-)- o4 am)&e Bal*al)ne 2#&rol#-)-0
= )4 &)lute ac)& )- a&&e& to t2e car!o"#late -alt8 t2e car!o"#l)c ac)& are 4orme&3

C
%arboxylic acid
R
C
O3
O
%arboxylate ion
H
>
R C OH
O
2:
benzoyl chloride
H
2
O
C Cl
O
E+am!le 1
C O C CH
+
CH
+
O O
ethanoic anhydride
H
2
O
21
ethyl ethanoate
H
2
O
H
>
E+am!le 1
C O CH
+
CH
+
O
22
&
'he reacti<ity o- a car*o+ylic acid deri<ati<e de!end)
on the *a)icity o- the )#*)tit#ent (lea<in( (ro#!) that
attached to the acyl (ro#!
&
'he le)) *a)ic the )#*)tit#ent, the more reacti<e the
car*o+ylic acid deri<ati<e3
Relat)9e React)9)t# O4 Car!o"#l)c Ac)&
Der)9at)9e-
23
Cl
@
J RCOO
@
J RO
@
J HO
@
J NH
2
@
Relat)9e !a-)c)t)e- o4 t2e lea9)n$ $rou% B-u!-t)tuent0
acid
chloride
acid
anhydride
ester carboxylic
acid
aide
react)9)t# )ncrea-e-
R C Cl
O
C O C R
O
R
O
C OR R
O
R C NH
2
O
R C OH
O
8 8 8 8
24
ACYL CHLORIDE
&
Ac#l c2lor)&e )- t2e mo-t react)9e *eca#)e o- it)
electro%o-)t)9e car!on#l $rou% i) attac2 to the
electrone$at)9e Cl atom (/hich i) a relea)in( (ro#!),
2%
ANHYDRIDE ACID
&
An2#&r)&e ac)& )- more react)9e t2an e-ter an&
am)&e *eca#)e the car*o+yl (ro#! o- anhydride i)
attached to the car*onyl car*on,

&
'hi) make) the car*onyl car*on *ecome) more
electro!o)iti<e and can !e ea-)l# attac* !#
nucleo%2)le3
R C O
O
C RF
O
22
ESTER
&
E-ter )- le-- react)9e to/ard) n#cleo!hile *eca#)e the
&elocal),at)on o- electron make) the !o)iti<e char(e o-
car*on can *e -2)4te& to o+y(en,
&
'hat make) the car!on#l car!on le-- electro%o-)t)9e3
C O
C H
3
O R
C
C
O
3
C H
3
O R
C O
3
C H
3
O
C
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24
AMIDE
&
Am)&e )- t2e lea-t react)9e *eca#)e, NH2 (ro#! i) an
electron=&onat)n$ (ro#! that make) the car*onyl le--
electro%o-)t)9e,
&
'he re-onance -tructure o- amide )ho/) that the
car!on#l car!on )- not electro%o-)t)9e3
0
R
O H
H
0
C
R
O
3
H
H
26
'he G)e) o- Car*o+ylic Acid
Car*o+ylic acid ? deri<ati<e) G)e)
olyamide (0ylon) car!et, a!!arel
E)ter Arti-icial -la<or)
Acetic acid $ine(ar
Ethanoic anhydride =r#( a)!irin
Halicylic acid anal(e)ic