SENYAWA

KARBONIL
ASAM KARBOKSILAT

Athina Mardatillah, M.Farm., Apt.

Department of Pharmaceutical of Analysis
Faculty of Pharmacy – Universitas Jenderal Achmad Yani
 carboxyl group
Esters carboxylic acids

methanoic acid
STRUKTUR
The carboxyl carbon atom is sp2-hybridized, and three of its valence electrons form three σ bonds
at 120° angles to one another (Figure DILOXANIDE
11.1).FOne
URANOATE σ bonds
of the(AN ) a hydrogen atom or a carbon
is to
ANTIBIOTIC
atom of an alkyl, aromatic, or heterocyclic group. The other two σ bonds are to oxygen atoms: one
CARBOXYLIC ACIDS to theInhydroxyl
this chapter we will
oxygen atom consider
and thetheother
structure,
to theproperties,
carbonyl and reactions
oxygen atom.ofTh
carboxylic acids.
e carbonyl Theseatom
carbon
ACYL GROUPS • Senyawa asam
compounds
of the carboxyl karboksilat
have
group
a carboxyl group memiliki
bonded to agugus
also has one electron in a 2p orbitalkarboksil
forming a πyang
hydrocarbon unit that can terikat
be saturated,
bond with pada in a 2p
unsaturated,
an electron
aromatic, or heterocyclic.
hidrokarbon jenuh,
orbital of the carbonyl tidak
oxygen jenuh, aromatik atau heterosiklik.
atom.
Although the bond angles at the carboxyl carbon atom are all approximately 120°, the carboxyl
O O O
group is often represented with only vertical and horizontal lines. To save space, two condensed rep-
resentations of the carboxyl C group
O are H commonly
R C used. O Unless
H required
Ar C to account
O H for the mechanism
of a reaction, the nonbonding electrons are not shown.
carboxyl group carboxylic acids

R C O H or R COOH or R CO2H

Equivalent representations of carboxylic acids

nic Chemistry. http://dx.doi.org/10.1016/B978-0-12-802444-7.00011-2 methanoic acid

Elsevier Inc. All rights reserved. The carboxyl carbon atom is sp2-hybridized, and three of its valence electrons form three σ bonds 287
at 120° angles to one another (Figure 11.1). One of the σ bonds is to a hydrogen atom or a carbon
atom of an alkyl, aromatic, or heterocyclic group. The other two σ bonds are to oxygen atoms: one
to the hydroxyl oxygen atom and the other to the carbonyl oxygen atom. The carbonyl carbon atom
 TATA NAMA ASAM KARBOKSILAT
• Asam karboksilat dan derivatnya ditemukan di alam dan merupakan senyawa
organik pertama yang diisolasi. Kerana senyawa ini telah diketahui sangat
lama, asam yang umum , ester dan senyawa asil lainnya memiliki nama yang
umum. Contoh asam yang umum seperti asam formic (HCO2H), asam asetat
(CH3CO2H), dan asam benzoat (C6H5CO2H)
 O
O N O

H
lactone lactam
(a cyclic ester) (a cyclic amide)

11.2 NOMENCLATURE OF Common Names

CARBOXYLIC ACIDS
The carboxylic acids and their derivatives are abundant in nature and were among the first organic

TATA NAMA ASAM KARBOKSILAT

substances to be isolated. Because they have been known for so long, the common acids, esters, and
other acyl compounds are often referred to by their common names. Some common acids are formic
acid (HCO2H), acetic acid (CH3CO2H), and benzoic acid (C6H5CO2H). Both the common and the
IUPAC names of a few commonly encountered carboxylic acids are given in Table 11.1.
Table 11.1
Nomenclature of Carboxylic Acids
Formula Common Name IUPAC Name
HCO2H Formic acid Methanoic acid
CH3CO2H Acetic acid Ethanoic acid
CH3CH2CO2H Propionic acid Propanoic acid
CH3(CH2)2CO2H Butyric acid Butanoic acid
CH3(CH2)3CO2H Valeric acid Pentanoic acid
CH3(CH2)4CO2H Caproic acid Hexanoic acid
CH3(CH2)6CO2H Caprylic acid Octanoic acid
CH3(CH2)10CO2H Lauric acid Dodecanoic acid
CH3(CH2)12CO2H Myristic Tetradecanoic acid
CH3(CH2)14CO2H Palmitic Hexadecanoic acid
CH3(CH2)16CO2H Stearic Octadecanoic acid

In common names of carboxylic acids and their derivatives, the positions of groups attached to the
parent chain are designated alpha (α), beta (β), gamma (γ), delta (δ), and so forth. The —COOH
group itself is not designated by a Greek letter.

Br CH2CH3 O

CH3 CH CH CH2 C OH
δ γ β α
 CH3CO2H Acetic acid Ethanoic acid
CH3CH2CO2H Propionic acid Propanoic acid
CH3(CH2)2CO2H Butyric acid Butanoic acid
CH3(CH2)3CO2H Valeric acid Pentanoic acid
CH3(CH2)4CO2H Caproic acid Hexanoic acid
CH3(CH2)6CO2H Caprylic acid Octanoic acid

TATACHNAMA ASAM KARBOKSILAT

CH3(CH2)10CO2H
(CH2)12CO2H Myristic
3
Lauric acid
Tetradecanoic acid
Dodecanoic acid

CH3(CH2)14CO2H Palmitic Hexadecanoic acid

CH3(CH2)16CO2H Stearic Octadecanoic acid
• Pada penamaan umum asam karboksilat dan derivatifnya, posisi gugus terikat
dengannames
In common rantaiof utama ditandai
carboxylic dengan
acids and huruf yunani
their derivatives, yaitu, alpha
the positions (a), attached
of groups beta (b),to the
gamma
parent chain are (g),designated
delta (δ),alpha
dan(α),
seterusnya. Gugus(γ),
beta (β), gamma —COOH tidak
delta (δ), and so ditandai
forth. Thedengan
—COOH
grouphuruf
itself istersebut.
not designated by a Greek letter.

Br CH2CH3 O

CH3 CH CH CH2 C OH
δ γ β α
β-bromo-γ-ethylvaleric acid

11.2 Nomenclature of Carboxylic Acids 289

 TATA NAMA ASAM KARBOKSILAT
• Asam karboksilat
Some unbranched carboxylic acids contain a —COOH group at each end of the chain. The common
yang tidak bercabang mengandung gugus -COOH pada
names and IUPAC names of some of these dicarboxylic acids are listed in Table 11.2.
ujung cincin.
Table 11.2
Nomenclature of Dicarboxylic Acids
Formula IUPAC Name Common Name
HO2C—CO2H Ethanedioic acid Oxalic acid
HO2C—CH2—CO2H Propanedioic acid Malonic acid
HO2C—(CH2)2—CO2H Butanedioic acid Succinic acid
HO2C—(CH2)3 —CO2H Pentanedioic acid Glutaric acid
HO2C—(CH2)4 —CO2H Hexanedioic acid Adipic acid

IUPAC Names of Carboxylic Acids

The IUPAC rules to name carboxylic acids are similar to those for aldehydes. The final -e of the par-
ent hydrocarbon is replaced by the ending -oic acid. The carboxyl group has a higher priority than
aldehyde, ketone, halogen, hydroxyl, and alkoxy groups. The priority order for carbonyl groups is
carboxylic acid > aldehyde > ketone. The carbonyl group of an aldehyde or ketone is indicated by
the prefix oxo-. Compounds that have a —CO2H group bonded to a cycloalkane ring are named as
 Some unbranched carboxylic acids contain a —COOH group at each end of the chain. The common
names and IUPAC names of some of these dicarboxylic acids are listed in Table 11.2.

Table 11.2
Nomenclature of Dicarboxylic Acids
Formula IUPAC Name Common Name
HO2C—CO2H Ethanedioic acid Oxalic acid
HO2C—CH2—CO2H Propanedioic acid Malonic acid
HO2C—(CH2)2—CO2H Butanedioic acid Succinic acid
HO2C—(CH2)3 —CO2H Pentanedioic acid Glutaric acid

TATA NAMA ASAM KARBOKSILAT

HO2C—(CH2)4 —CO2H Hexanedioic acid Adipic acid

IUPAC Names of Carboxylic Acids

The IUPAC rules to name carboxylic acids are similar to those for aldehydes. The final -e of the par-
• ent hydrocarbon
Syarat penamaan asam karboksilat secara isIUPAC
replacedmirip
by the dengan
ending -oicaldehid.
acid. TheAkhiran
carboxyl group has a hidrokarbon
–a pada higher priority than
aldehyde, ketone, halogen, hydroxyl, and alkoxy groups. The priority order for carbonyl groups is
diganti dengan akhiran –oic
acid. Gugus karboksil memiliki prioritas
carboxylic acid utama daripada
> aldehyde > ketone.aldehid, keton,
The carbonyl grouphalogen, hidroksil
of an aldehyde danisgugus
or ketone alkoksi.
indicated by Urutan prioritas
gugus karbonil menjadi asamthekarboksilat > aldehidthat
prefix oxo-. Compounds > have
keton. Gugusgroup
a —CO2H karbonil
bondeddarito a suatu aldehid
cycloalkane atau
ring are keton
named as ditandai dengan awalan
derivatives of the cycloalkane, and the suffix -carboxylic acid is added. The ring carbon atom
oxo-. Senyawa yang memiliki gugus —CO2H yang terikat pada cincin sikloalkana dinamakan sebagai derivatid dari sikloalkana dan to which
the carboxyl carbon atom is bonded is assigned the number 1, but this number is not included in the
ditambah akhiran –carboxylic name.
acid. Cincin aomexamples
The following karbonillustrate
yang merupakan
the IUPAC rules atom karbon
for naming karboksil
carboxylic acids.yang terikat diberi penomoran 1,
tetapi angka ini tidak disebutkan dalam penamaan. Contohnya:
OH CH3 O O CH3 O
CH3 CH CH C OH CH3 C CH C OH
4 3 2 1 4 3 2 1
3-hydroxy-2-methylbutanoic acid 2-methyl-3-oxobutanoic acid

CH3 O Cl

CH3 CH C C C OH
5 4 3 2 1
CO2H
4--methyl-2-pentynoic acid
cis-2-chlorocyclohexanecarboxylic acid

Names of Carboxylic Acid Derivatives

The name of the conjugate base of a carboxylic acid, a carboxylate anion, is obtained by changing the
-oic acid ending to -oate. For a salt of a carboxylic acid, the name of the carboxylate anion is preceded
by the name of the metal ion.

O O
 3 O CH3 O
CH3 CH CH C OH CH3 C CH C OH
4 3 2 1 4 3 2 1
3-hydroxy-2-methylbutanoic acid 2-methyl-3-oxobutanoic acid

CH3 O Cl

CH3 CH C C C OH
5 4 3 2 1
CO2H
4--methyl-2-pentynoic acid

Nama-nama Derivat Asam Karboksilat

Names of Carboxylic Acid Derivatives
cis-2-chlorocyclohexanecarboxylic acid

The name of the conjugate base of a carboxylic acid, a carboxylate anion, is obtained by changing the
• -oic acid
Nama dariending
basatokonjugat
-oate. For a salt
asamof a carboxylic acid, the
karboksilat, name of
suatu the carboxylate
anion anion is didapatkan
karboksilat, preceded
by the name of the metal ion.
dengan mengganti akhiran -oic acid dengan -oate. Untuk garam asam karboksilat,
nama dari anion karboksilat diawali dengan nama ion logamnya.
O O

CH3 C O Na CH2 CH2 C O K

sodium ethanoate potassium 3-phenylpropanoate

(sodium acetate) (potassium β-phenylpropionate)

• Suatu ester diberi nama dengan penulisan awalanny nama gugus alkil atau aril yang
An ester is named by first writing the name of the alkyl or aryl group bonded to the bridging oxygen
terikat
atom,menjembatani atom
followed by the name of theoksigen,
acyl portiondiikuti dengan
of the ester, which nama
is derivedbagian asil dariacid
from a carboxylic ester, yang
merupakan
and named asderivat dari asam karboksilat dan dinamakan sebagai karboksilat.
a carboxylate.

hapter 11 Carboxylic Acids and Esters

 O O

CH3CH2 CH2 C O CH2 CH3 CH2 CH2 C O CH2 CH2 CH3

Nama-nama Derivat Asam Karboksilat

ethyl butanoate propyl-3-cyclohexylpropanoate
(propyl-β-cyclohexylpropionate)

O O

CH2CH2CH2 C Br C Cl

4-phenylbutanoyl bromide cyclopentanecarbonyl chloride

An acid anhydride consists of two acyl groups bonded through a bridging oxygen atom. Although
acid anhydrides can have O O acyl groups are
two different acyl groups, compounds containing identical
more common. They are named by replacing the suffix -oic acid with -oic anhydride.
CH3CH2 CH2 C O CH2 CH3 CH2 CH2 C O CH2 CH2 CH3
O O O O
ethyl butanoate propyl-3-cyclohexylpropanoate
CH3CH2CH2 C O C CH2CH2CH3 C O C
(propyl-β-cyclohexylpropionate)

butanoic anhydride benzoic anhydride

O O
Amides are named by replacing theCH suffix for the acid
2CH2CH2 C (-oic
Br acid) with the suffix -amide.
C An Cl amide
functional group bonded to a cycloalkane ring is named as a carboxamide.
4-phenylbutanoyl bromide cyclopentanecarbonyl chloride
O O
 O O

CH3CH2 CH2 C O CH2 CH3 CH2 CH2 C O CH2 CH2 CH3

ethyl butanoate propyl-3-cyclohexylpropanoate

(propyl-β-cyclohexylpropionate)

Nama-nama Derivat Asam Karboksilat

O O

CH2CH2CH2 C Br C Cl
• Suatu asam anhidrida teriri dari dua gugus asil yang terikat pada jembatan
atom oksigen. Meskipun 4-phenylbutanoyl
asambromide
anhidrida dapat memiliki cyclopentanecarbonyl
dua gugus chloride
asil yang
berbeda, senyawa
An acid anhydrideini jugaofdapat
consists mengandung
two acyl gugusaasil
groups bonded through yangoxygen
bridging sama. atom. Although
acid anhydrides
Penamaannya can havemengganti
dengan two different acyl groups,-oic
akhiran compounds containing
acid dengan -oicidentical acyl groups are
anhydride.
more common. They are named by replacing the suffix -oic acid with -oic anhydride.

O O O O

CH3CH2CH2 C O C CH2CH2CH3 C O C

butanoic anhydride benzoic anhydride

Amides are named by replacing the suffix for the acid (-oic acid) with the suffix -amide. An amide
functional group bonded to a cycloalkane ring is named as a carboxamide.

O O

CH2CH2 C NH2 C NH2

 4-phenylbutanoyl bromide cyclopentanecarbonyl chloride

An acid anhydride consists of two acyl groups bonded through a bridging oxygen atom. Although
acid anhydrides can have two different acyl groups, compounds containing identical acyl groups are
more common. They are named by replacing the suffix -oic acid with -oic anhydride.

O O O O

CH3CH2CH2 C O C CH2CH2CH3 C O C
Nama-nama Derivat Asam Karboksilat
butanoic anhydride benzoic anhydride

•Amides
Amida diberi by
are named nama dengan
replacing mengganti
the suffix akhiran
for the acid -oicwith
(-oic acid) acidthe
dengan -amide.AnGugus
suffix -amide. amide
functional
fungsi group
amidabonded to adengan
terikat cycloalkane ring issikloalkana
cincin named as a carboxamide.
dan diberi nama carboxamide.
O O

CH2CH2 C NH2 C NH2

3-phenylpropanamide cyclohexanecarboxamide

•In Pada amida

secondary sekunder
and tertiary danthetersier,
amides, atom
nitrogen atomnitrogen terikat
is bonded to one ordengan satu
more alkyl ataugroups
or aryl lebih
gugus
instead alkil atauatoms.
of hydrogen aril sebagai gantinya
We will discuss atom ofhidrogen.
the names amides with groups bonded to nitrogen
along with the names of amines in Chapter 14.

Problem 11.1
The structure of oleic acid, an unsaturated carboxylic acid present as an ester in vegetable oils, is
shown below. What is the IUPAC name of oleic acid?
 O O

CH2CH2 C NH2 C NH2

3-phenylpropanamide cyclohexanecarboxamide

In secondary and tertiary amides, the nitrogen atom is bonded to one or more alkyl or aryl groups
instead of hydrogen atoms. We will discuss the names of amides with groups bonded to nitrogen
along with the names of amines in Chapter 14.
Contoh soal
Problem 11.1
• TheThe
structure
structure of oleicacid,
of oleic acid, an unsaturated
an unsaturated carboxylic
carboxylic acid
acid present as present
an ester inasvegetable
an esteroils, is
in vegetable oils,
shown below. is isshown
What below.
the IUPAC nameWhat
of oleicisacid?
the IUPAC name of oleic acid?
CH3 (CH2 )6 CH2 CH2 (CH2 )6 CO2 H
C C
H H

Solution
• First, determine the length of the continuous chain that contains the —COOH group. It contains 18
carbon atoms. The double bond is located at C-9, numbering from the carboxyl group on the right.
Thus, the compound is a 9-octadecenoic acid. The configuration about the double bond is Z, and
therefore the complete name is (Z)-9-octadecenoic acid.

Problem 11.2
Mevalonic acid is required to form isopentenyl pyrophosphate, an intermediate in terpene synthesis.
It has the following structure. What is its IUPAC name?
 Jawaban
• Pertama tentukan panjang rantai yang mengandung gugus —COOH.
Senyawa tersebut mengandung 18 atom karbon. Lokasi ikatan rangkap
berada di nomor C-9, penomoran gugus karboksil dari kanan. Sehingga
namanya menjadi 9-octadecenoic acid.
 When a substituent is linked to an acyl group through a sulfur atom, the derivative is called a thioester.
Thioesters are less reactive than acid chlorides and acid anhydrides, but they are sufficiently reactive to
participate in many biochemical acyl transfer reactions.

Gugus Asil dan Derivat Asam Karboksilat O

R C S R
thioester

• Ester, amida,
Esters, amides, anhidrida
anhydrides, dan tioester
and thioesters memungkinkan
may make up berbentuk
part of a cyclic structure. Cyclic esters siklik.
are calledEster
siklik disebut
lactones. sebagai
Cyclic amides lakton.
are called lactams.Amida siklik
Cyclic acyl disebut
derivatives behavelaktam.
chemically like acyclic acyl
compounds.

O
O N O

H
lactone lactam
(a cyclic ester) (a cyclic amide)

NCLATURE OF Common Names

IC ACIDS
The carboxylic acids and their derivatives are abundant in nature and were among the first organic
substances to be isolated. Because they have been known for so long, the common acids, esters, and
other acyl compounds are often referred to by their common names. Some common acids are formic
acid (HCO2H), acetic acid (CH3CO2H), and benzoic acid (C6H5CO2H). Both the common and the
IUPAC names of a few commonly encountered carboxylic acids are given in Table 11.1.
orbital of the carbonyl carbon
atom and an electron of the 2p orbitals of
sp3 hybrid orbital of the carbon and oxygen
oxygen atom form a σ bond
σ bond
An electron of the sp2 hybrid
orbital of the carbonyl carbon
atom and an electron of the
Gugus Asil dan Derivat Asam Karboksilat
sp2 hybrid orbital of the
oxygen atom form a σ bond

The Acyl Group and Carboxylic Acid Derivatives

• Bagian “RCO” mengandung asam karboksilat yang disebut gugus asil.
Beberapa
The “RCO” unit derivatif
containedasam mengandung
in a carboxylic acidgugus oksigen
is called atau
an acyl atom Several families of acid
group.
elektronegatif,
derivatives seperti nitrogen
have oxygen-containing groupsatau halogen, yang atoms,
or electronegative menempati gugus
such as OH or a halogen,
nitrogen
in placepada
of the OHkarboksilat.
asam group of a carboxylic
Gugus iniacid. This group,
digambarkan represented
sebagai by dapat
L, yang L, candiganti
be replaced in a
nucleophilic
dengan acyl substitution
reaksi reaction
nukleofilik (Section
subtitusi asil. 11.6).
O O

CH3 C L + Nu CH3 C Nu + L

If an alkoxy (–OR) or phenoxy (– OAr) group is bonded to the acyl group, the derivative is an ester.
Esters are formed from a carboxylic acid and an alcohol in a condensation reaction (Section 11.8).
Esters are moderately reactive toward water in hydrolysis reactions and produce a carboxylic acid and
an alcohol (Section 11.9).

O O O
The Acyl Group and Carboxylic Acid Derivatives

The “RCO” unit contained in a carboxylic acid is called an acyl group. Several families of acid
derivatives have oxygen-containing groups or electronegative atoms, such as nitrogen or a halogen,
in place of the OH group of a carboxylic acid. This group, represented by L, can be replaced in a
nucleophilic acyl substitution reaction (Section 11.6).

Gugus Asil
O dan Derivat Asam Karboksilat
O

CH3 C L + Nu CH3 C Nu + L

If an• alkoxy
Jika gugus
(– OR)alkoksi (–OR)
or phenoxy (–atau fenoksi
OAr) group is (–OAr)
bonded terikat pada
to the acyl gugus
group, theasil,
derivative is an ester.
Esters derivatif
are formed yang
fromterbentuk disebut
a carboxylic ester.
acid and an Ester
alcoholterbentuk dari asam
in a condensation karboksilat
reaction (Section 11.8).
Esters dengan reaksi reactive
are moderately kondensasi. Ester
toward waterbersifat cukupreactions
in hydrolysis bereaksiand
dengan
produceairapada
carboxylic acid and
an alcohol (Section
reaksi 11.9).
hidrolisis dan menghasilkan asam karboksilat dan alkohol.
O O O

R C O R! R C O Ar Ar C O Ar!

Examples of esters (acyl groups shown in red)

If the substituent is linked to the acyl group through a nitrogen atom, the compound is called an
amide. The classification of amides depends on the number of carbon groups, including the acyl
group, bonded to the nitrogen atom. These compounds are much less reactive than esters in hy-
drolysis reactions. The amide functional group is responsible for the structural stability of proteins
(Chapter 14). We will discuss amides in Chapter 12.
 O O

CH3 C L + Nu CH3 C Nu + L

If an alkoxy (–OR) or phenoxy (– OAr) group is bonded to the acyl group, the derivative is an ester.
Esters are formed from a carboxylic acid and an alcohol in a condensation reaction (Section 11.8).
Esters are moderately reactive toward water in hydrolysis reactions and produce a carboxylic acid and
an alcohol (Section 11.9).

O O O

Gugus Asil
R C dan
O Derivat
R! R C OAsam
Ar Ar Karboksilat
C O Ar!

Examples of esters (acyl groups shown in red)

• Jika suatu
If the substituent is linked to the
cabang terhubung acyl group
dengan through
gugus asila dengan
nitrogen atom, the compound
adanya is called an
atom nitrogen,
amide. The classification of amides depends on the number of carbon groups, including the acyl
makagroup,
senyawa
bonded initodisebut amida.
the nitrogen atom. Klasifikasi
These compoundsamida bergantung
are much dari
less reactive nomor
than esters in hy-
gugusdrolysis
karbon, termasuk
reactions. gugus
The amide asil, yang
functional terikat
group is padaforatom
responsible nitrogen.
the structural Senyawa
stability of proteins
(Chapter
ini lebih tidak 14).reaktifdaripada
We will discuss amides
esterin pada
Chapterreaksi
12. hidrolisis.

O O O

R C N H R C N R' R C N R'

H H R'
primary amide secondary amide tertiary amide

When the substituent attached to an acyl group is a chlorine atom, the derivative is called an acid chlo-
ride or acyl chloride. When two acyl groups are bonded to a common oxygen atom, the compound is
an acid anhydride. Neither of these highly reactive compounds occurs in nature, but they are used in
the laboratory synthesis of esters and amides.

O O O
 Examples of esters (acyl groups shown in red)

If the substituent is linked to the acyl group through a nitrogen atom, the compound is called an
amide. The classification of amides depends on the number of carbon groups, including the acyl
group, bonded to the nitrogen atom. These compounds are much less reactive than esters in hy-
drolysis reactions. The amide functional group is responsible for the structural stability of proteins
(Chapter 14). We will discuss amides in Chapter 12.

GugusR Asil dan

C N H
Derivat
R
O
Asam
C N R' R
Karboksilat
C N R'
O O

H H R'
• Apabila subtituen yang terhubung
primary amide di gugus
secondary amide asil berupatertiary
atomamide
klorin, maka
derivatif ini disebut dengan asam klorida atau asil klorida. Sedangkan
When the substituent attached to an acyl group is a chlorine atom, the derivative is called an acid chlo-
terdapat dua gugus asil terikat pada atom oksigen, senyawa ini disebut asam
ride or acyl chloride. When two acyl groups are bonded to a common oxygen atom, the compound is
ananhidrida. Kedua
acid anhydride. Neithersenyawa ini memiliki
of these highly reaktifitas
reactive compounds yang
occurs tinggibutdithey
in nature, alam,
are used in
the laboratory synthesis
seringnya digunakan of esters
padaandlaboratorium
amides. untuk sintetsi ester atau amida.
O O O

R C Cl R C O C R
acid chloride acid anhydride

Carboxylic Acids and Esters

 Gugus Asil dan Derivat Asam Karboksilat
• Saat subtituen atom sulfur terhubung dengan gugus asil, maka derivatif ini
dibesut isdengan
When a substituent linked tioester. Tioester
to an acyl group kereaktifannya
through lebihthelemah
a sulfur atom, daripada
derivative asam
is called a thioester.
Thioesters areklorida dan asam
less reactive thananhidrida, tetapi
acid chlorides senyawa
and ini reaktifbut
acid anhydrides, pada reaksi
they transfer
are sufficientlyasil
reactive to
participate insecara
manybiokimia.
biochemical acyl transfer reactions.
O

R C S R
thioester

Esters, amides, anhydrides, and thioesters may make up part of a cyclic structure. Cyclic esters are called
lactones. Cyclic amides are called lactams. Cyclic acyl derivatives behave chemically like acyclic acyl
compounds.
 SIFAT FISIKA
1. Wujud
Pada temperatur ruangan, asam karboksilat yang bersuku rendah (C1 – C4) berwujud cair yang encer, yang bersuku tengah (C5- C9)
berwujud zat cair yang kental, sedangkan asam karboksilat bersuku tinggi (C > 10) berwujud padat yang tidak dapat larut begitu saja
dalam air.
2. Titik Didih dan Titik leleh
Adanya ikatan hidrogen anatar molekulnya menjadikan titik didih dan titik leleh asam karboksilat relatif tinggi. Ada gaya tarik menarik
yang kuat antar molekulnya. Asam format (H-COOH) memiliki titik didih 101o C , asam asetat (CH3-COOH) memiliki titik didih 118o C,
dan asam propianat (C2H5-COOH) memiliki titik didih 141o C. Semakin panjang rantai C nya maka semakin tinggi titik didih dan titik
leburnya.
3. Kelarutan
Hanya asam karaboksilat suku rendah yang dapat dilarutkan sempurna dalam air, sedangkan suku tengah dan suku tinggi sifatnya sukar
larut dalam air.
4. Daya hantar listrik
Karena proses ionisasi yang terjadi ketika dilarutkan meupakan ionisasi sebagian maka asam karboksilat ketika dilarutkan dalam air akan
menghasilkan larutan elektrolit lemah. Larutan ini juga kurang bagus dalam menghantarkan arus listrik.
 2

CH3 C O H CH3 C CH3 CH3 C CH3

bp 118 oC bp 56.5 oC bp –7 oC

Table 11.3
Physical Properties of Carboxylic Acids
IUPAC Name Melting Boiling Solubility in Water
Point (oC) Point (oC) (g/100 mL at 20 oC)
Methanoic acid 101 Miscible
Ethanoic acid 118 Miscible
Propanoic acid 141 Miscible
Butanoic acid 164 Miscible
Pentanoic acid 186 4.97
Hexanoic acid 205 0.960
Octanoic acid 239 0.068
Decanoic acid 32 270 0.015
Dodecanoic acid 44 299 0.0055

Carboxylic acids with low molecular weights are soluble in water because the carboxyl group forms
several hydrogen bonds with water. A carboxylic acid acts both as a hydrogen bond donor through its
hydroxyl hydrogen atom and as a hydrogen bond acceptor through the lone pair electrons of both oxy-
gen atoms. The solubility of carboxylic acids, like that of alcohols, decreases with increasing chain length
because the long, nonpolar hydrocarbon chain dominates the physical properties of the acid.
Table 11.4
Physical Properties of Esters
IUPAC Name Boiling Point (oC) Solubility (g/100 mL H2O)
Methyl methanoate 32 Miscible
Methyl ethanoate 57 24.4
Methyl propanoate 80 1.8
Methyl butanoate 102 0.5
Methyl pentanoate 126 0.2
Methyl hexanoate 151 0.06

Ethyl methanoate 54 Miscible

Ethyl ethanoate 77 7.4
Ethyl propanoate 99 1.7
Ethyl butanoate 120 0.5
Ethyl pentanoate 145 0.2

Propyl ethanoate 102 1.9

Butyl ethanoate 125 1.0

Methyl benzoate 199 0.1

Ethyl benzoate 213 0.08

Table 11.5
Esters Used As Flavoring Agents
IUPAC Name Formula Flavor
Methyl butanoate CH3CH2CH2CO2CH3 Apple
Pentyl butanoate CH3CH2CH2CO2CH2(CH2)3CH3 Apricot
Pentyl ethanoate CH3CO2CH2(CH2)3CH3 Banana
Octyl ethanoate CH3CO2CH2(CH2)6 CH3 Orange
Ethyl butanoate CH3(CH2)2CO2CH2CH3 Pineapple
 SIFAT KIMIA
1. Ikatan kimia
Asam karboksilat mengandung ikatan yang disebut ikatan hidrogen. Ikatan ini
menghubungkan antar molekul senyawa asam tersebut.
2. Kepolaran
Karena memiliki gugus hidroksil yang memiliki sifat polar maka asam karboksilat termasuk
kedalam kelompok senyawa polar.
3. Kereaktifan
Tingkat kereaktifan asam karboksilat semakin menurun seiring dengan peningkatan jumlah
atom karbon. Makin tinggi sukunya maka akan semakin tidak reaktif.
 CO2
predominates over the metabolism of carbohydrates. CO When2 there is not
citrate
react with all of the acetyl coenzyme A being produced, acetyl coenzym
Claisen condensation.
Most of the acetyl coenzyme A produced in this and other metabolic reac
acetic acid to form citric acid. However, in certain illnesses, such as diabetes
O predominatesO over the metabolism of carbohydrates. O When there is notOeno
react with all of the acetyl coenzyme A being produced, acetyl coenzyme A
CH3 C S CoA + CH3 condensation.
Claisen C S CoA CH3 C CH2 C
O O O acetoacetyl-C
O

CH3 Hydrolysis
C S of the
CoA + CHresulting C β-keto
S thioester yields
CoA CH3 acetoacetic
C CH2 acid C (3-kS
Sintesis Asam Karboksilat dengan Metode
3
quent reactions produce 3-hydroxybutanoic acid and acetone, which are
acetoacetyl-CoA
bodies. Detection
Hydrolysisofofthese compounds
the resulting β-keto in the urine
thioester yieldsindicates
acetoaceticdiabetes.
acid (3-keto

Oksidatif quent reactions produce 3-hydroxybutanoic acid and acetone, which are co
bodies. Detection of these compounds in the urine indicates diabetes.
SUMMARY OF REACTIONS
1. Synthesis of SUMMARY OF REACTIONS
Carboxylic Acids by Oxidative Methods (Section 11.5)
1. Synthesis of Carboxylic Acids by Oxidative Methods (Section 11.5)
Jones reagent
CH2CH2OH Jones reagent CH2CO2H
CH2CH2OH CH2CO2H

CH3 CH3 CO2H CO2H

KMnO4
KMnO4

OCH2CH3 OCH2CH3
OCH2CH3 OCH2CH3

Summary

Summ
Sintesis Asam Karboksilat dari Haloalkana
2. Synthesis of Carboxylic Acids from Haloalkanes (Section 11.5)
2. Synthesis of Carboxylic Acids from Haloalkanes (Section 11.5)
O
O
Br 1. Mg/ether C
Br 1. Mg/ether
2. CO C
OH
2
2. CO OH
3. H3O+ 2
CH3 3. H3O+ CH3
CH3 CH3
o-bromotoluene o-methylbenzoic acid
o-bromotoluene o-methylbenzoic acid
CH2Br CH2CO2H
1. KCN
CH2Br CH2CO2H
2. H +
1.3 O
KCN
2. H3 O+
3. Synthesis of Acyl Halides (Section 11.6)
O O
3. Synthesis of Acyl Halides (Section 11.6)
SOCl2
CH2 C OH CH2 C ClO
O
SOCl2
CH
4. Reduction of C Acids
Carboxylic
2 OH and Acid Derivatives (SectionCH
11.7)
2 C Cl
O
4. Reduction of Carboxylic Acids
1. LiAlHand
4 Acid Derivatives (Section 11.7)
CH2 C OH CH2 CH2OH
2. H3O+
O
2. Synthesis of Carboxylic Acids from Haloalkanes (Section 11.5)
O

Br 1. Mg/ether C
2. CO2 OH
3. H3O+
CH3 CH3

o-bromotoluene o-methylbenzoic acid

Sintesis Asil Halida

CH2Br CH2CO2H
1. KCN
2. H3 O+

3. Synthesis of Acyl Halides (Section 11.6)

O O
SOCl2
CH2 C OH CH2 C Cl

4. Reduction of Carboxylic Acids and Acid Derivatives (Section 11.7)

O
1. LiAlH4
CH2 C OH CH2 CH2OH
2. H3O+

C CH2OH
OCH3 1. LiAlH4
+ CH3OH
2. H3O+

O O
 2. CO2 OH
o-bromotoluene 3. H3O+ o-methylbenzoic acid
3. H3O+
CH CH
CH33 CH3 3
o-bromotoluene
CH2Br CH CO2H
2
o-methylbenzoic acid
o-bromotoluene o-methylbenzoic acid
1. KCN
CH2Br
CH2
Br 2. H3 O+ CHCO
CH2
2CO
2H
2H

1.1.KCN
KCN
2.2.HH3 O++
3O
3. Synthesis of Acyl Halides (Section 11.6)
3. Synthesis
3. Synthesisof
ofAcyl
AcylHalides
Halides (Section11.6)
O (Section 11.6) O

Reduksi Asam Karboksilat dan Derivatif Asam

CH22
CH
O
CH2 O C
CC OH
OH
OH
SOCl
SOCl
SOCl2
2 2
CH
CH
OO
CH2
2 2 C C Cl Cl
C Cl

4. Reduction of Carboxylic Acids and Acid Derivatives (Section 11.7)

Reductionof
4. Reduction ofCarboxylic
CarboxylicAcids
Acidsand
andAcid
AcidDerivatives
Derivatives (Section
(Section 11.7)
11.7)
OO
O
1.4 LiAlH4
1.1.LiAlH
LiAlH 4
CH
CH
CH22 2 CC COH
OHOH CH2 2 CH
CH 2CH
CHOH
2OH
2 CH2OH
2.2.HH
3O
+ +
2.
3O H3O+

O
OO
CC CH
CH2OH
2OH
C OCH
OCH33 1.1.LiAlH 4
CH2OH
OCH3 2. HLiAlH 4
1.+ LiAlH
O + 4
+ +CH3OH
CH3OH
3 O
2. H3 + CH3OH
2. H3O+
O O
O O
CO C O
C Cl CH
Cl 1. LiAlH[(OC(CH3)]3 H
1. LiAlH[(OC(CH3)]3
C 2. H3O+ + C
2. H3O
Cl 1. LiAlH[(OC(CH3)]3 H
5. Synthesis of Esters (Sections
2. 11.6
H11.6and
+ 11.8)
5. Synthesis of Esters (Sections 3O and 11.8)
CH3 O CH3 CH3 O CH3
CH3 O CH3 H3O+ CH3 O CH3
5.CH
Synthesis
3 C CH of2 Esters
OH (Sections
+ HO C C 11.6CHand
3 11.8)
H 3O +
CH3 C CH2 O C C CH3
CH3 C CH2 OH + HO C C CH3 CH3 C CH2 O C C CH3
HCH3 HO CH3 H CH3 H O CH3
H H H3O + H H
O CH3 CH3 O CH3
CH3 C CH2 OH + HOO CCH 3
C CH 3
pyridine CHCH
3 3 C CH
O 2 CHO
3
C C CH3
CH2 OH + Cl C C CH3 pyridine CH3 C CH2 O C C CH3
 O 1. LiAlH4
O
CH2 C OH 1. LiAlH
+ 4 CH2 CH2OH
CH2 C OH2.1. H 3O 4
LiAlH CH2 CH OH
CH2 C OH 2. H+3O+ CH2 CH2OH2
2. H3O
O
OO
C CH2OH
C COCH3 1. LiAlH4 CHCH
2OH
2OH
OCH3
OCH 1. LiAlH + CH3OH
3 1. H
2. O+ 4 4
LiAlH + CH 3OH
3
H+3O+
+ CH3OH
2. H2.3O
O O
OO O O
C C
C CCl
Cl Cl Sintesis Ester
1. LiAlH[(OC(CH3)]3
1. H
2.
1. LiAlH[(OC(CH
LiAlH[(OC(CH
3O
+
+
)]
3)]3 3 3
C CH
H H
2. H2.3O
H3O
+

5. Synthesis of Esters (Sections 11.6 and 11.8)

5. 5. Synthesis
Synthesis of of Esters
Esters (Sections
(Sections 11.6
11.6 andand 11.8)
11.8)
CH3 O CH3 CH3 O CH3
CHCH
3 3 O
O CH3 3 CH H 3O + CH
CH3 3 O OCH3CH3
CH3 C CH2 OH + HO C C CH3 H
H3O 3+ O +
CH3 C CH2 O C C CH3
CHCH3 3 C C CH CH
2 2 OH OH + HO C C C C CHCH
+ HO 3 3 CH3CH3C CCH2CH2O OC CC CCH3CH3
H H H H
HH H H H H H H
O CH3 CH3 O CH3
O O CHCH3 3 pyridine CH3CH3 O OCH3CH3
CH2 OH + Cl C C CH3 pyridine pyridineCH3 C CH2 O C C CH3
CHCH 2 2 OH OH+ Cl
+ Cl C C C C CHCH 3 3 CH3CH3C CCH2CH2O OC CC CCH3CH3
H H H
H H H H H H
OH O O O CH3
OHOH O O O O – O OC CH3CH3
OH C C
+ CH3 C O C CH3 OH–OH–
+ + CHCH 3 3 C C O O C C CHCH 3 3 O
CH3 CH 3
O O
CHCH3 3 CH3CH3

310 Chapter 11 Carboxylic Acids and Esters

310
310 Chapter Carboxylic
11 11
Chapter Acids
Carboxylic andand
Acids Esters
Esters
 Kondensasi Klaisen
6. Claisen Condensation (Sections 11.9)

CH6.
3
Claisen Condensation
O CH3 (Sections 11.9) CH3 O CH3
H3O+
CH3 C CH2 CH
O3 C C O 3 CH3
CH CH3 C CH2 CH
OH3 + HO C C O 3 CH3
CH
H3O+
H CH3 C CH2 HO C C CH3 H CH3 C CH2 OH + HO
H C C CH3

O H H O H H
H3O+
C O 3
OCH2CH C O– + O
CH3CH2OH
H3O+
O C OCH2CH3 O C O– + CH3CH2OH
7. Claisen Condensation
O (Sections 11.9) O
7. Claisen O
Condensation (Sections 11.9) O H O
1. CH3CH2O–
CH2 C OCH2O
CH3 CH2 C C CO H 2O
OCH CH3
2. H3O+ 1. CH3CH2 O–
CH2 C OCH2CH3 CH2 C C C OCH2CH3
2. H3O+

EXERCISES
6. Claisen Condensation (Sections 11.9)

CH3 O CH3 CH3 O CH3

H3O+
CH3 C CH2 O C C CH3 CH3 C CH2 OH + HO C C CH3

H H H H
O

C OCH2CH3
Kondensasi Klaisen
H3O+
O

C O– + CH3CH2OH
O O
7. Claisen Condensation (Sections 11.9)

O O H O
1. CH3CH2 O–
CH2 C OCH2CH3 CH2 C C C OCH2CH3
2. H3O+

EXERCISES
Nomenclature

11.1 Give the common name for each of the following acids:
(a) CH3CH2CO2H (b) CH3(CH2)4CO2H (c) CH3(CH2)16CO2H

11.2 Draw the structure of each of the following esters:

(a) octyl acetate (b) ethyl butyrate (c) propyl valerate
11.3 Give the IUPAC name for each of the following esters:
 Kegunaan
a. Asam format atau yang dikenal juga dengan nama asam semut digunakan sebagai bahan baku pembasmi hama dan
berperan besar dalam proses penggumpalan lateks.
b. Asam asetat
– di dalam industri, asam asetat digunakan sebagai bahan baku sintesis serat dan juga plastik.
– digunakan sebagai pelarut dan pereaksi dalam laboratorium
– digunakan sebagai cuka makanan (kadar 3-6%)
c. Asam Oksalat
– Ditemukan dalam daun bayam dan buah-buahan, bentuk senyawanya berupa garam natrium dan kalsium
– dapat digunakan untuk menghilangkan karat dan juga digunakan sebagai bahan baku pembuatan zat warna.
– mengasamkan minuman, permen, dan bahan makanan lainnya.
– sering digunakan dalam fotografi, keramik, dan proses penyamakan kulit.
d. Asam sitrat banyak digunakan sebagai bahan untuk pengawetan buah dalam kaleng.
e. Asam stearat merupakan salah satu bahan penting dalam pembuatan lilin.
 Ethyl propanoate 99 1.7
Ethyl butanoate 120 0.5
Ethyl pentanoate 145 0.2

Propyl ethanoate 102 1.9

Butyl ethanoate 125 1.0

Methyl benzoate
Ethyl benzoate
Kegunaan
199
213
0.1
0.08

Table 11.5
Esters Used As Flavoring Agents
IUPAC Name Formula Flavor
Methyl butanoate CH3CH2CH2CO2CH3 Apple
Pentyl butanoate CH3CH2CH2CO2CH2(CH2)3CH3 Apricot
Pentyl ethanoate CH3CO2CH2(CH2)3CH3 Banana
Octyl ethanoate CH3CO2CH2(CH2)6 CH3 Orange
Ethyl butanoate CH3(CH2)2CO2CH2CH3 Pineapple
Ethyl methanoate HCO2CH2CH3 Rum

ACIDITY OF Although acetic acid and other carboxylic acids are weak acids, they are much more acidic than alco-
BOXYLIC ACIDS hols or phenols. The acid ionization constant, Ka, for acetic acid is about 1011 times larger than the Ka
for ethanol.

CH3CH2OH + H2O CH3CH2O + H3O Ka = 1 ! 10–16

CH3CO2H + H2O CH3CO2 + H3O Ka = 1.8 ! 10–5

The greater acidity of acetic acid is the result of resonance stabilization of the negative charge in the
conjugate base, acetate ion. In the ethoxide ion (CH3CH2O−) the negative charge is concentrated on
a single oxygen atom.