Sovia Aprina Basuki

KIMIA ORGANIK II
FARMASI UMM
2018
 Asam karboksilat dan turunannya (2)
 Senyawa nitrogen organik (2)
 Karbohidrat (2)
 Lipid, fosfolipid dan prostaglandin
 Terpenoid dan steroid
 Asam amino, protein dan asam nukleat (2)
 Warna dan zat warna
 Spektroskopi senyawa organik (2)
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
 Organic Chemistry, 7th edition, John McMurry
 Organic Chemistry, T. W. Graham Solomons
 Organic Chemistry, Fessenden and
Fessenden
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).
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.
The two most important features of the carbonyl group are:

· Because oxygen is more electronegative than either carbon or hydrogen, the

C—O and O—H bonds are polar.
 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 butyric acid
CH3CH2CH2CH2CO2H pentanoic acid valeric acid

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Carboxylic acids, common names:
…
CH3(CH2)4CO2H caproic acid
CH3(CH2)5CO2H enanthic acid
CH3(CH2)6CO2H caprylic acid
CH3(CH2)7CO2H pelargonic acid
CH3(CH2)8CO2H capric acid
CH3(CH2)9CO2H undecyclic acid
CH3(CH2)10CO2H lauric acid
CH3(CH2)11CO2H tridecyclic acid
CH3(CH2)12CO2H myristic acid
CH3(CH2)13CO2H pentadecyclic acid
CH3(CH2)14CO2H palmitic acid
CH3(CH2)15CO2H margaric acid
CH3(CH2)16CO2H stearic acid
 ω

6 5 4 3 2 1

Cl O Ph
CH3CH2CHC OH CH3CH2CH2CHCH2COOH
-chlorobutyric acid -phenylcaproic acid
 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)

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 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)

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 COOH
special names

benzoic acid

COOH COOH COOH

CH3

CH3
CH3

o-toluic acid m-toluic acid p-toluic acid

COOH

CH(CH3)2

COOH

OH
 COOH

CH(CH3)2
2-isopropylcyclopentanecarboxylic acid

COOH

OH
o-hydroxybenzoic acid (salicylic acid)
 Br
HOOCCH2CHCH2CH2COOH

3-bromohexanedioic acid
-bromoadipic acid
salts of carboxylic acids:
name of cation + name of acid: drop –ic acid, add –ate

CH3CO2Na sodium acetate or sodium ethanoate

CH3CH2CH2CO2NH4 ammonium butyrate

ammonium butanoate

(CH3CH2COO)2Mg magnesium propionate

magnesium propanoate
 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)

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 Fluoroacetic, chloroacetic, bromoacetic, and
iodoacetic acids are stronger acids than acetic acid
 Multiple electronegative substituents have synergistic
effects on acidity

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 If pKa of given acid and the pH of the medium are known, % of
dissociated and undissociated forms can be calculated using the
Henderson-Hasselbalch eqn

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The Inductive Effect in Aliphatic Carboxylic Acids

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25
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 acidic—The conjugate base is destabilized
because electron density is being donated to a negatively
charged carboxylate anion.

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[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.

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

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 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.
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 air.

2. Titik didih dan titik leleh

Asam karboksilat membentuk ikatan hidrogen Rumus Struktur Td
berupa siklik dimer antarmolekul. Ikatan H-COOH 101
hidrogen yang kuat ini menyebabkan TD dan TL CH3-COOH 118
lebih tinggi dari alkohol yang bersesuaian. CH3-CH2-COOH 141
CH3-CH2-CH2-COOH 163
CH3-CH2-CH2-CH2- 187
COOH
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 dalam air, sehingga
termasuk senyawa elektrolit lemah. - +
R-COOH ⇋ R-COO + H
[1] Oxidation of 1° alcohols

[2] Oxidation of alkyl benzenes

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[3] Oxidative cleavage of alkynes

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1. Reaksi dengan Basa (penyabunan)

R-COOH + NaOH → R-COONa + H2O

sabun
2. Reaksi esterifikasi
H2SO4
R-COOH + R’-OH → R-COOR’ + H2O
Asam karboksilat Alkohol Ester

3. Reaksi dengan PCl5

R-COOH + PCl5 → R-CO-Cl + POCl3 + HCl
Alkanoilklorida
4. Reaksi dengan NH3
R-COOH + NH3 → R-CONH2 + H2O
Amida
5. Reaksi dengan Cl2
CH3-CH2-COOH + Cl2 → R-CHCl-COOH + HCl
Asam 2-monokloropropanoat
Reactions of Carboxylic Acids

The most important reactive feature of a carboxylic acid is its polar O—H
bond, which is readily cleaved with base.
• The nonbonded electron pairs on oxygen create electron-rich sites
that can be protonated by strong acids (H—A).
• 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 C—O 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 Acids—Strong Organic BrØnsted-Lowry Acids

• Carboxylic acids are strong organic acids, and as such, readily react
with BrØnsted-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.

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• Carboxylic acids are relatively strong acids because
deprotonation forms a resonance-stabilized conjugate base—a
carboxylate anion.

• The acetate anion has two C—O bonds of equal length (1.27 Å)
and intermediate between the length of a C—O single bond
(1.36 Å) and C=O (1.21 Å).
• 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 O—H
bonds—namely 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 H—A more acidic.
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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 isophthalic acid
terephthalic acid

H COOH H COOH
C C
C C
H COOH HOOC H

maleic acid fumaric acid