Carboxilic Acids

Chapter 20
(McMurry)
Organic Chemistry II QUIM 3463
Dr. Carlos Nieves Marrero

Capsaicin
 ____________

_____

Organic Chemistry; Smith, J.G., 4th Ed., 2014

20.1
Nomenclatura: Ácidos Carboxílicos
1. Tomar la cadena mas larga que incluya el
carbonilo.
2. El carbono del carbonilo es el C-1
3. Nombre base: ácido ______ óico
4. Los grupos sustituyentes se identifican
siguiendo las reglas y se colocan después de
la palabra ácido.
20.1
Nomenclatura: Ácidos Carboxílicos
5. Enlaces múltiples en un ácido carboxílico
– Ácido ______x-enóico
– Ácido ______x-inóico
• x es la posición del enlace múltiple
• cis/trans y E/Z en enlaces dobles
6. Si el carbonilo esta unido a un anillo:
– ácido __ciclo____carboxílico
– ácido __bencenocarboxílico
20.1
Nomenclatura: Ácidos Carboxílicos
7. Si hay 2 grupos –COOH se utiliza el prefijo di
(-dioico ó -dicarboxílico)
8. Cuando hay una cetona en la misma cadena;
el carbonilo de la cetona se identifica con la
palabra oxo.
Si la cetona está en una cadena sustituyente es un grupo
x ____oil (x es la posición del carbonilo)
9. Cuando hay un aldehído este se toma como
un sustituyente formil.
 (20.2) Structure & Properties of Carboxylic Acid

• 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.

9
Organic Chemistry; Smith, J.G., 4th Ed., 2014
 Bonds in Carboxylic Acids

• The C–O single bond of a carboxylic acid is shorter than the

C–O bond of an alcohol.
• This can be explained by looking at the hybridization of the
respective carbon atoms.

• Because oxygen is more electronegative than either carbon

or hydrogen, the C–O and O–H bonds are polar.
10
Organic Chemistry; Smith, J.G., 4th Ed., 2014
 Hydrogen Bonds Cause Dimers

• Carboxylic acids exhibit dipole–dipole interactions

because they have polar C–O and O–H bonds.
• They also exhibit intermolecular hydrogen bonding.
• Carboxylic acids often exist as dimers held together by
two intermolecular hydrogen bonds.
Two molecules of acetic acid
(CH3COOH) held together by
two hydrogen bonds

11
Organic Chemistry; Smith, J.G., 4th Ed., 2014

12
 Dissociation of Carboxylic Acids
• Carboxylic acids are proton donors toward weak and
strong bases
– Produces metal carboxylate salts, RCO2– M+
• Carboxylic acids with more than six carbons are slightly
soluble in water
– Conjugate base salts are water-soluble
 Acidity Constant and pKa
• Carboxylic acids transfer a proton to water to
give H3O+ and carboxylate anions, RCO2-
• Acidity constant, Ka, is about 10-4 to 10-5 for a
typical carboxylic acid
– Gives the extent of acidity dissociation

- +
[RCO2 ][H3O ]
Ka = and pK a = - log K a
[RCO2 H]
Table 20.3 - Acidity of Some Carboxylic Acids
 Acid–Base 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.

16
Organic Chemistry; Smith, J.G., 4th Ed., 2014
 Protonation of Carboxylic Acids
• 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.

17
Organic Chemistry; Smith, J.G., 4th Ed., 2014
 Reaction with Nucleophiles and Bases
• 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 p bond as well.

• Carboxylic acids are strong organic acids, and as such,

readily react with BrØnsted–Lowry bases to form carboxylate
anions.

18
Organic Chemistry; Smith, J.G., 4th Ed., 2014
 Deprotonation of Carboxylic Acids
• 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.

19
Organic Chemistry; Smith, J.G., 4th Ed., 2014
 Resonance of Carboxylate Anions
• 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).

20
Organic Chemistry; Smith, J.G., 4th Ed., 2014
 21
Organic Chemistry; Smith, J.G., 4th Ed., 2014
 Acidity of Common Organic Acids
• 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.
22
Organic Chemistry; Smith, J.G., 4th Ed., 2014
 Acidity of Ethanol
• 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.
Organic Chemistry; Smith, J.G., 4th Ed., 2014

Figure 20-1

23
 Acidity of Phenol
• 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.

24
Organic Chemistry; Smith, J.G., 4th Ed., 2014
Energies of Resonance Structures for Phenoxide
Figure 19.6

• Structures 2–4 have the negative charge on a C atom, a less

electronegative element than O, making them less stable than
structures 1 and 5.
• Structures 1 and 5 have intact aromatic rings, whereas structures
2–4 do not, making structures 1 and 5 more stable.
25
Organic Chemistry; Smith, J.G., 4th Ed., 2014
Acidity of Acetic Acid
 Relationship Between Acidity and Stability of Conjugate Base

Figure 19.7
• Resonance
stabilization of the
conjugate base is
important in
determining acidity,
the absolute
number of
resonance
structures alone is
not what is
important!

27
Organic Chemistry; Smith, J.G., 4th Ed., 2014
 Inductive Effects in Carboxylic Acids

28
Organic Chemistry; Smith, J.G., 4th Ed., 2014
 Inductive Effects in Carboxylic Acids

29
Organic Chemistry; Smith, J.G., 4th Ed., 2014
 (19.11) Substituent Effects in Aromatic Carboxylic Acids
• 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.

30
Organic Chemistry; Smith, J.G., 4th Ed., 2014
 Substituent Effects in Aromatic Carboxylic Acids
[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.

31
Organic Chemistry; Smith, J.G., 4th Ed., 2014
 Common Substituent Effects

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

32
Organic Chemistry; Smith, J.G., 4th Ed., 2014
 Preparation of Carboxylic Acids
[1] Oxidation of 1° alcohols

[2] Oxidation of alkyl benzenes

34
Organic Chemistry; Smith, J.G., 4th Ed., 2014
 Preparation of Carboxylic Acids
[3] Oxidative cleavage of alkynes

[4] Carboxylation of Grignard reagents

35
Organic Chemistry; Smith, J.G., 4th Ed., 2014
 Preparation of Carboxylic Acids
[5] Hydrolysis of nitriles

36
 Some General
Reactions of Carboxylic Acids