Organic Chemistry, 7th Edition

L. G. Wade, Jr.

Chapter 20
Ácidos carboxílicos

Copyright © 2010 Pearson Education, Inc.

Sesión 13

En esta sesión responderemos a las cuatro

preguntas marco para los ácidos carboxílicos.
Dentro de su reactividad veremos sus derivados
más conocidos y con mayor aplicación.
1. TIPO DE COMPUESTO ORGÁNICO
 Introduction
 The functional group of carboxylic acids
consists of a C═O with —OH bonded to
the same carbon.
 Carboxyl group is usually written —COOH.
 Aliphatic acids have an alkyl group bonded
to —COOH.
 Aromatic acids have an aryl group.
 Fatty acids are long-chain aliphatic acids.
Chapter 20 2
 IR Bands of Carboxylic Acids

 There will be two features in the IR spectrum of a

carboxylic acid: the intense carbonyl stretching
absorption (1710 cm-1) and the OH (2500–
absorption
 3500 cm-1) . band.
Conjugation lowers the frequency of the C═O
Chapter 20 26
 IR Spectroscopy

O—H
C═O
Chapter 20 27
2. DÓNDE ESTÁN Y PROPIEDADES
Hydrolysis of Fats and Oils

• The basic hydrolysis of fat and oils produces soap

(this reaction is known as saponification).
Chapter 20 23
Extraction of Carboxylic Acids
 Some Important Acids
 Acetic acid is in vinegar and other
foods, used industrially as solvent,
catalyst, and reagent for synthesis.
 Fatty acids from fats and oils.
 Benzoic acid in found in drugs and
preservatives.
 Adipic acid used to make nylon 66.
 Phthalic acid used to make polyesters.
Chapter 20 25
 Structure of Formic Acid

 The sp2 hybrid carbonyl carbon atom is planar, with

nearly trigonal bond angles.
 The O—H bond also lies in this plane, eclipsed with
the C═O bond.
 The sp3 oxygen has a C—O—H angle of 106°.
Chapter 20 8
Resonance Structures of Formic Acid

El efecto resonante estabiliza

la estructura de un ácido
carboxílico haciendo que su
 Carbon is sp2 hybridized. anión se estabilice también,
 Bond angles are close to 120 . por ello tiene carácter ácido
(bajo pKa)
 O—H eclipsed with C═O, to get overlap of
orbital with orbital of lone pair on oxygen.
Chapter 20 9
 p.e.

 Higher boiling points than similar alcohols,

due to the formation of a hydrogen-bonded
dimer.
Chapter 20 10
 p.f.
 Aliphatic acids with more than 8
carbons are solids at room temperature.
 Double bonds (especially cis) lower the
melting point. The following acids all
have 18 carbons:
 Stearic acid (saturated): 72 C
 Oleic acid (one cis double bond): 16 C
 Linoleic acid (two cis double bonds): -5 C

Chapter 20 11
 Solubility
 Water solubility decreases with the length of the
carbon chain.
 With up to 4 carbons, acid is miscible in water.
 Very soluble in alcohols.
 Also soluble in relatively nonpolar solvents like
chloroform because the hydrogen bonds of the
dimer are not disrupted by the nonpolar solvent.

Chapter 20 12
 Acidity of Carboxylic Acids

 A carboxylic acid may dissociate in water to give a

proton and a carboxylate ion.
 The equilibrium constant Ka for this reaction is
called the acid-dissociation constant.
 The acid will be mostly dissociated if the pH of the
solution is higher than the pKa of the acid.
Chapter 20 13
 Acetate Ion Structure

 Each oxygen atom bears half of the negative charge.

 The delocalization of the negative charge over the
two oxygens makes the acetate ion more stable than
an alkoxide ion.
Chapter 20 15
 Substituent Effects on Acidity

• The magnitude of a substituent effect depends on its distance from

the carboxyl group.
Chapter 20 16
 Aromatic Carboxylic Acids

 Electron-withdrawing groups enhance the acid

strength and electron-donating groups decrease the
acid strength.
 Effects are strongest for substituents in the ortho and
para positions.
Chapter 20 17
Values of Ka and pKa for Substituted Carboxylic Acids

Acid

F3CCOOH 5.9 X 10-1 0.23 .

2.3 X 10-1 _ stronger acids
Cl3CCOOH 0 64
Cl2CHCOOH 5.5 X 10-2 1.26
02N-CH2COOH 2.1 X 10-2 1.68
NCCH2COOH 3.4 X 10-3 2.46
FCH2COOH 2.6 X 10-3 2.59
CICH2COOH 1.4 X 10-3 2.86
CH3CH2CHCICOOH 1.4 X 10-3 2.86
BrCH2COOH 1.3 X 10-3 2.90
ICH2COOH 6.7 X 10-4 3.18
CH30CH2COOH 2.9 X 10-4 3.54
HOCH2COOH 1.5 X 10-4 3.83
CH3CHCICH2COOH 8.9 X 10-5 4.05
PhCOOH 6.46 X 10-s 4.19
PhCH2COOH 4.9 X 10-5 4.31
CICH2CH2CH2COOH 3.0 X 10-5 4.52
CH3COOH 1.8 X 10-5 4.74
CH3CH2CH2COOH 1.5 X 10-5 4.82
Copyright© 201 O Pearson Prentice Hall, lnc.

Chapter 20 18
Deprotonation of Carboxylic Acids

Las sales generadas son más

solubles en agua

 The hydroxide ion deprotonates the acid to

form the acid salt.
 Adding a mineral acid regenerates the
carboxylic acid.
Chapter 20 20
Se nombran con la
terminación ato
 First name the cation.
 Then name the anion by replacing the
-ic acid with -ate.
Cl
- +
CH3CH2CHCH2COO K

3-cloropentanoato de potasio

Chapter 20 21
3. DIVERSIDAD ESTRUCTURAL Y
NOMENCLATURA
 Common Names

 Many aliphatic acids have historical names.

 Positions of substituents on the chain are
labeled with Greek letters starting at the
carbon attached to the carboxylic carbon.
Chapter 20 3
 IUPAC Names

 Remove the final -e from alkane name, add

the ending -oic acid.
 The carbon of the carboxyl group is #1.
Chapter 20 4
 Unsaturated Acids

 Remove the final -e from alkene name, add

the ending -oic acid.
 Stereochemistry is specified.

Chapter 20 5
 Aromatic Acids

 Aromatic acids are named as derivatives of benzoic

acid.
 Ortho-, meta- and para- prefixes are used to specify
the location of a second substituent.
 Numbers are used to specify locations when more
than 2 substituents are present.
Chapter 20 6
 Dicarboxylic Acids
 Aliphatic diacids are usually called by
their common names.
 For IUPAC name, number the chain from
the end closest to a substituent.

Br
HOOCCH2CHCH2CH2COOH

3-bromohexanedioic acid
-bromoadipic acid

Chapter 20 7
4. REACTIVIDAD
4.1. Síntesis
4.2. Reactividad
 Synthesis Review
 Oxidation of primary alcohols and
aldehydes with chromic acid.
 Cleavage of an alkene with hot KMnO4
produces a carboxylic acid if there is a
hydrogen on the double-bonded
carbon.
 Alkyl benzene oxidized to benzoic acid
by hot KMnO4 or hot chromic acid.
Chapter 20 32
1. Oxidation of Primary Alcohol to
Carboxylic Acids

 Primary alcohols and aldehydes are commonly

oxidized to acids by chromic acid formed
(H2CrO4
 from Na2Cr2O7 and H2SO4). used, but
Potassium permanganate is occasionally 33
the yields are often lower.
Chapter 20
2. Cleavage of Alkenes Using KMnO4

 Warm, concentrated permanganate solutions oxidize

the glycols, cleaving the central C═C bond.
 Depending on the substitution of the original double
bond, ketones or acids may result.

Chapter 20 34
3. Alkyne Cleavage Using Ozone or
KMnO4

 With alkynes, either ozonolysis or a vigorous

permanganate oxidation cleaves the triple
bond to give carboxylic acids.
Chapter 20 35
4. Side Chain Oxidation of
Alkylbenzenes

Chapter 20 36
5. Conversion of Grignards to
Carboxylic Acids

 Grignard reagent react with CO2 to produce, after protonation, a

carboxylic acid.
 This reaction is sometimes called “CO2 insertion” and it
increases the number of carbons in the molecule by one.
Chapter 20 37
 6. Hydrolysis of Nitriles

CH2Br CH2CN CH2CO2H

+
NaCN H , H2 O
acetone

 Basic or acidic hydrolysis of a nitrile (—CN)

produces a carboxylic acid.
 The overall reaction, starting from the alkyl
halide, adds an extra carbon to the molecule.
Chapter 20 38
4. REACTIVIDAD
4.1. Síntesis
4.2. Reactividad
 Acid Derivatives
 The group bonded to the acyl carbon
determines the class of compound:
 —OH, carboxylic acid
 —Cl, acid chloride
 —OR’, ester
 —NH2, amide
 These interconvert via nucleophilic acyl
substitution.
Chapter 20 39
 Nucleophilic Acyl Substitution

 Carboxylic acids react by nucleophilic acyl

substitution, where one nucleophile replaces
another on the acyl (C═O) carbon atom.
Chapter 20 40
 1. Fischer Esterification

 Reaction of a carboxylic acid with an alcohol under acidic

conditions produces an ester.
 Reaction is an equilibrium, the yield of ester is not high.
 To drive the equilibrium to the formations of products use a
large excess of alcohol.
Chapter 20 41
Fischer Esterification Mechanism

 Step 1:
 The carbonyl oxygen is protonated to activate the carbon
toward nucleophilic attack.
 The alcohol attacks the carbonyl carbon.
 Deprotonation of the intermediate produces the ester
hydrate.
Chapter 20 42
Fischer Esterification Mechanism

 Step 2:
 Protonation of one of the hydroxide creates a good leaving
group.
 Water leaves.
 Deprotonation of the intermediate produces the ester.

Chapter 20 43
Cuando la esterificación ocurre
en la misma molécula:
Lactonas son ésteres cíclicos
Esterificaciones en cadena:
Polimerización de ésteres:
poliésteres (ej. PET)
 2. Synthesis of Amides

 The initial reaction of a carboxylic acid with an amine

gives an ammonium carboxylate salt.
 Heating this salt to well above 100° C drives off
steam and forms an amide.
Chapter 20 48
Lactamas son amidas cíclicas
Polimerización de amidas:
poliamidas (ej. Nailon)
3a. LiAlH4 or BH3 Reduction of
Carboxylic Acids a Alcoholes

 LiAlH4 reduces carboxylic acids to primary alcohols.

 The intermediate aldehyde reacts faster with the reducing agent
than the carboxylic acid.
 BH3•THF (or B2H6) can also reduce the carboxylic acid to
the
alcohol 49
Chapter 20
3b.Reducción de ácidos
carboxílicos a aldehidos

 Lithium aluminum tri(tert-butoxy)hydride is a weaker reducing

agent than lithium aluminum hydride.
 It reduces acid chlorides because they are strongly activated
toward nucleophilic addition of a hydride ion.
 Under these conditions, the aldehyde reduces more slowly, and
it is easily isolated.
Chapter 20 50
4. Conversión del ácido carboxílico
a cetona

 A general method of making ketones involves

the reaction of a carboxylic acid with two
equivalents of an organolithium reagent.
Chapter 20 51
 Mechanism of Ketone Formation

OLi OH
O O
+
2 R' Li H3O
R C OH R C OLi R C OH R C R' + H2O
R' R'

dianion hydrate of ketone ketone

 The first equivalent of organolithium acts as a base,

deprotonating the carboxylic acid.
 The second equivalent adds to the carbonyl.
 Hydrolysis forms the hydrate of the ketone, which
converts to the ketone.
Chapter 20 52
6. Síntesis de cloruros de ácido

El reactivo de cloruro es uno de los mejores

reactivos para conseguir el cloruro de ácido
 Mechanism of Acid Chloride
Formation
Step 1

Step 2

Step 3

Chapter 20 54
6a.Esterification of an Acid Chloride

 Attack of the alcohol at the electrophilic carbonyl

group gives a tetrahedral intermediate. Loss of a
chloride and deprotonation gives an ester.
 Esterification of an acyl chloride is more efficient than
the Fischer esterification.
Chapter 20 55
 6b.Amide Synthesis

 Ammonia and amines react with acid chlorides to

give amides
 NaOH, pyridine, or a second equivalent of amine is
used to neutralize the HCl produced to prevent
protonation of the amine.

Chapter 20 56
RESUMEN

Ácidos carboxílicos: qué son, dónde los

encontramos, cuáles son sus propiedades, cómo se
sintetizan y cómo al reaccionar generan derivados
con aplicación biológica e industrial.

TAREA

Hoja de ejercicios de Sesión. Ejercicios adicionales

de Wade.