ASAM KARBOKSILAT

Sovia Aprina Basuki

KIMIA ORGANIK II
FARMASI UMM
2013

TUJUAN INSTRUKSIONAL
KHUSUS
Mahasiswa dapat:
Menggambarkan struktur asam karboksilat,
memberi nama asam karboksilat,
menjelaskan sifat keasaman
Menjelaskan konsep penarik dan pendorong elektron
Menjelaskan efek orto pada asam karboksilat aromatik,
menjelaskan sifat-sifat fisika asam karboksilat.
Menuliskan reaksi-reaksi pembuatan asam karboksilat
Menuliskan reaksi-reaksi asam karboksilat
Menuliskan rumus umum asam dikarboksilat
Menyebutkan sifat-sifat asam dikarboksilat

PUSTAKA

Organic Chemistry, 7th edition, John

McMurry
Organic Chemistry, T. W. Graham
Solomons
Organic Chemistry, Fessenden and
Fessenden

ACYL GROUP

ACYL GROUP

A general acyl group (blue) as an acylium ion (top centre), as an

acyl radical (top right), in a ketone (top left), an aldehyde (bottom
left), ester (bottom centre) or amide (bottom right). (R1, R2, R3 =
organyl substituents or hydrogen).

I. STRUKTUR ASAM KARBOKSILAT

Structure and Bonding
Carboxylic acids are compounds containing a carboxy
group (COOH).
The structure of carboxylic acids is often abbreviated
as RCOOH or RCO2H, but keep in mind that the central
carbon atom of the functional group is doubly bonded
to one oxygen atom and singly bonded to another.

STRUCTURE AND BONDING

The two most important features of the carbonyl group are:

Because oxygen is more electronegative than either

carbon or hydrogen, the CO and OH bonds are polar.

II. TATA NAMA ASAM KARBOKSILAT

Carboxylic Acids, R-COOH

If derived from open-chain alkanes, replace the
terminal -e of the alkane name with -oic acid
The carboxyl carbon atom is C1

Common names:

IUPAC

Common

HCO2H

methanoic acid

formic acid

CH3CO2H

ethanoic acid

acetic acid

CH3CH2CO2H

propanoic acid

propionic acid

CH3CH2CH2CO2H

butanoic acid

CH3CH2CH2CH2CO2H

pentanoic

butyric acid

valeric acid

CCCCC=O

used in common names

Carboxylic acids, common names:

CH3(CH2)4CO2H

caproic acid

CH3(CH2)5CO2H

---

CH3(CH2)6CO2H

caprylic acid

CH3(CH2)7CO2H

---

CH3(CH2)8CO2H

capric acid

CH3(CH2)9CO2H

---

CH3(CH2)10CO2H

lauric acid

ALTERNATIVE NAMES

Compounds with CO2H bonded to a ring are named

using the suffix -carboxylic acid
The CO2H carbon is not itself numbered in this
system
Use common names for formic acid (HCOOH) and
acetic acid (CH3COOH)

11

COOH

special names

benzoic acid

COOH
CH3

COOH

CH3
o-toluic acid

m-toluic acid

COOH

CH3
p-toluic acid

salts of carboxylic acids:

name of cation + name of acid: drop ic acid, add ate
CH3CO2Na

sodium acetate

CH3CH2CH2CO2NH4

or sodium ethanoate

ammonium butyrate

ammonium butanoate
(CH3CH2COO)2Mg

magnesium propionate

magnesium propanoate

III. KEASAMAN ASAM

KARBOKSILAT

Carboxylic acids transfer a proton to water to give

H3O+ and carboxylate anions, RCO2, but H3O+ is a
much stronger acid
The acidity constant, Ka,, is about 10-5 for a typical
carboxylic acid (pKa ~ 5)

15

INDUCTIVE EFFECTS ON
ACIDITY

Fluoroacetic, chloroacetic, bromoacetic, and

iodoacetic acids are stronger acids than acetic acid
Multiple electronegative substituents have
synergistic effects on acidity

17

BIOLOGICAL ACIDS AND THE

HENDERSON-HASSELBALCH EQUATION

If pKa of given acid and the pH of the medium

are known, % of dissociated and undissociated
forms can be calculated using the HendersonHasselbalch eqn

18

IV. PENGARUH GUGUS PENARIK DAN PENDORONG ELEKTRON

The Inductive Effect in Aliphatic Carboxylic Acids

19

20

V. EFEK ORTO PADA ASAM KARBOKSILAT AROMATIK

Substituted Benzoic Acids

Recall that substituents on a benzene ring either donate or

withdraw electron density, depending on the balance of their
inductive and resonance effects. These same effects also
determine the acidity of substituted benzoic acids.
[1] Electron-donor groups destabilize a conjugate base, making
an acid less acidicThe conjugate base is destabilized
because electron density is being donated to a negatively
charged carboxylate anion.

21

[2] Electron-withdrawing groups stabilize a conjugate base, making an

acid more acidic. The conjugate base is stabilized because
electron density is removed from the negatively charged
carboxylate anion.

22

Figure 19.8
How common substituents
affect the reactivity of a
benzene ring towards
electrophiles and the acidity of
substituted benzoic acids

23

Subtituen posisi orto dari turunan asam benzoat selalu

meningkatkan sifat keasaman senyawa tersebut karena
subtituen ini mengurangi resonansi luar cincin.
Efek orto pada asam benzoat tidak tergantung pada jenis
substituen apakah cenderung menarik atau melepaskan
elektron.
Efek resonansi sangat berpengaruh terhadap kekuatan
asam. Subtituen yang berada pada posisi orto akan
mengurangi resonansi luar cincin sehingga akan
meningkatkan kekuatan asam.
Senyawa turunan asam benzoat yang mempunyai
kekuatan asam tertinggi adalah senyawa turunan asam
benzoate yang subtituennya terletak pada posisi orto.

VI. SIFAT-SIFAT FISIK ASAM

KARBOKSILAT
1. Wujud
Pada temperatur kamar, asam karboksilat yang
bersuku rendah adalah zat cair yang encer, suku
tengah berupa zat cair yang kental, dan suku
tinggi berupa zat padat yang tidak larut dalam
2.air.
Titik didih dan titik leleh
Asam karboksilat membentuk
Rumus Struktur
ikatan hidrogen berupa siklik
H-COOH
dimer antarmolekul. Ikatan
CH3-COOH
hidrogen yang kuat ini
CH3-CH2-COOH
menyebabkan TD dan TL lebih
CH3-CH2-CH2-COOH
tinggi dari alkohol yang
CH3-CH2-CH2-CH2-COOH
bersesuaian.

Td
101
118
141
163
187

3. Kelarutan
Carboxylic acids are proton donors toward weak
and strong bases, producing metal carboxylate
salts, RCO2 + M
Carboxylic acids with more than six carbons are
only slightly soluble in water, but their conjugate
base salts are water-soluble

4. Daya hantar listrik

Asam karboksilat dapat terionisasi sebagian
dalamR-COOH
air, sehingga
termasuk
elektrolit
R-COO
+senyawa
H+
lemah.

VII. CARA PEMBUATAN ASAM KARBOKSILAT

[1]

Oxidation of 1 alcohols

[2]

Oxidation of alkyl benzenes

27

[3] Oxidative cleavage of alkynes

28

VIII. REAKSI-REAKSI ASAM

KARBOKSILAT
1. Reaksi dengan Basa (penyabunan)
R-COOH + NaOH R-COONa +
sabun
H 2O
2. Reaksi esterifikasi
H2SO4
R-COOH
+
R-OH
R-COOR
Asam
karboksilat
Alkohol
Ester
+ H2O
3. Reaksi dengan PCl5
R-COOH + PCl5 R-CO-Cl
+
Alkanoilklorida
+ HCl
4. Reaksi dengan NH3
R-COOH + NH3 R-CONH2 + H2O
Amida

POCl3

5. Reaksi dengan Cl2

CH3-CH2-COOH + Cl2 R-CHCl-COOH
+
Asam 2-monokloropropanoat
HCl

Reactions of Carboxylic Acids

The most important reactive feature of a carboxylic acid is its polar OH
bond, which is readily cleaved with base.

 The nonbonded electron pairs on oxygen create electron-rich

sites that can be protonated by strong acids (HA).
Protonation occurs at the carbonyl oxygen because the resulting
conjugate acid is resonance stabilized (Possibility [1]).
The product of protonation at the OH group (Possibility [2])
cannot be resonance stabilized.

 The polar CO bonds make the carboxy carbon electrophilic. Thus,

carboxylic acids react with nucleophiles.
Nucleophilic attack occurs at an sp2 hybridized carbon atom, so it
results in the cleavage of the bond as well.

Carboxylic AcidsStrong Organic Brnsted-Lowry Acids

Carboxylic acids are strong organic acids, and as such, readily react
with Brnsted-Lowry bases to form carboxylate anions.

 An acid can be deprotonated by a base that has a conjugate

acid with a higher pKa.
Because the pKa values of many carboxylic acids are ~5, bases
that have conjugate acids with pKa values higher than 5 are
strong enough to deprotonate them.

34

 Carboxylic acids are relatively strong acids because

deprotonation forms a resonance-stabilized conjugate basea
carboxylate anion.

The acetate anion has two CO bonds of equal length (1.27

) and intermediate between the length of a CO single bond
(1.36 ) and C=O (1.21 ).

 Ethoxide, the conjugate base of ethanol, bears a negative charge on

the O atom, but there are no additional factors to further stabilize
the anion. Because ethoxide is less stable than acetate, ethanol is a
weaker acid than acetic acid.

Phenoxide, the conjugate base of phenol, is more stable than

ethoxide, but less stable than acetate because acetate has two
electronegative O atoms upon which to delocalize the negative
charge, whereas phenoxide has only one.

Figure 19.7
Summary: The relationship
between acidity and conjugate
base stability for acetic acid,
phenol, and ethanol

Note that although resonance stabilization of the conjugate base is

important in determining acidity, the absolute number of resonance
structures alone is not what is important!

 Resonance stabilization accounts for why carboxylic

acids are more acidic than other compounds with OH
bondsnamely alcohols and phenols.

To understand the relative acidity of ethanol, phenol

and acetic acid, we must compare the stability of their
conjugate bases and use the following rule:
- Anything that stabilizes a conjugate base A: makes the
starting acid HA more acidic.
39

IX. ASAM DIKARBOKSILAT

HOOC-COOH

oxalic acid

HO2C-CH2-CO2H

malonic acid

HO2C-CH2CH2-CO2H

succinic acid

HO2C-CH2CH2CH2-CO2H

glutaric acid

HOOC-(CH2)4-COOH

adipic acid

HOOC-(CH2)5-COOH

pimelic acid

CO2H
CO2H

CO2H

CO2H

CO2H
CO2H

phthalic acid

H
H

C
C

isophthalic acid

terephthalic acid

COOH

COOH

HOOC

maleic acid

C
C

COOH
H

fumaric acid