BOOKS
1) Organic Chemistry Structure and Function, K.
Peter C. Vollhardt, Neil Schore, 6th Edition
2) Organic Chemistry, T. W. Graham Solomons,
Craig B. Fryhle
3) Organic Chemistry: A Short Course, H. Hart,
L. E. Craine, D. J. Hart, C. M. Hadad,
4) Organic Chemistry: A Brief Course, R. C.
Atkins, F.A. Carey
3. ALDEHYDES AND KETONES
3.1 Nomenclature of Aldehydes and Ketones
3.2 Synthesis of Aldehydes and Ketones
3.3 The Carbonyl Group
3.4 Nucleophilic Addition to the Carbon–Oxygen Double Bond
3.4.1 The Addition of Water
3.4.2 The Addition of Alcohols
3.4.3 The Addition of Hydrogen Cyanide and Sodium bisulfide
3.4.4 The Addition of Strong Nucleophile
3.4.5 The Addition of Primary and Secondary Amines
3.5 Oxidation and Reduction of Carbonyl Compounds
3.6 Keto-Enol Tautomerization
3.7 α-Hydrogen Acidity of Carbonyl Compounds; Enolate Anion
3.8 Aldol Condensation
3.9 Crossed Aldol Condensations
3. ALDEHYDES AND KETONES
Aldehydes and ketones both contain the carbonyl group—a group in
which a carbon atom has a double bond to oxygen. The carbonyl group
of an aldehyde is bonded to one hydrogen atom and one carbon atom
(except for formaldehyde, which is the only aldehyde bearing two
hydrogen atoms). The carbonyl group of a ketone is bonded to two
carbon atoms. Using R, we can designate the general formulas for
aldehydes and ketones as follows:
O O
R-C-H R-C-R
Aldehyde Ketone
3.1 Nomenclature of Aldehydes and Ketones
Aliphatic aldehydes are named substitutively in the IUPAC system by
replacing the final -e of the name of the corresponding alkane with -
al. Aliphatic ketones are named substitutively by replacing the final -
e of the name of the corresponding alkane with -one.
The chain is then numbered in the way that gives the carbonyl carbon
atom the lower possible number, and this number is used to designate
its position. Some aldehydes and ketones have common names that are
retained in the IUPAC system:
3.2 Synthesis of Aldehydes and Ketones
1. Oxidation of alcohols: The oxidation state of an aldehyde lies
between that of a 1° alcohol and a carboxylic acid. Aldehydes can be
prepared from 1° alcohols by oxidation with pyridinium chlorochromate
(C5H5NH+CrO3Cl-, or PCC). Ketones can be prepared from secondary
alcohols by oxidation.
[O]
RR1CH2OH RCHO
[O]
RR CHOH
1
RCOR
R1 = H, primary alcohol R1 = H, aldehyde
R1 = alkyl, seconder alcohol R1 = alkyl, ketone
[O]: KMnO4 / H2SO4; K2Cr2O7 /H2SO4
2. Aldehydes by Reduction of Acyl Chlorides, Esters, and Nitriles:
Acyl chlorides (RCOCl), esters (RCO2R1), and nitriles (RCN) are all
easily prepared from carboxylic acids, and they all are more easily
reduced. When any carboxylic acid derivatives are treated with
LiAlH4, they are reduced all the way to the 1° alcohol.
3. Ozonolysis of Alkenes: Alkenes can be cleaved by ozonolysis of
their double bond. The products are aldehydes and ketones.
4. Ketones from arenes by Friedel–Crafts acylations: Aromatic
ketones can be prepared from arenes by Friedel–Crafts acylations
3.3 The Carbonyl Group
Aldehydes and ketones have a trigonal planar arrangement of groups
around the carbonyl carbon atom. The carbon atom is sp2 hybridized.
The trigonal planar arrangement of groups around the carbonyl carbon
atom means that the carbonyl carbon atom is relatively open to attack
from above or below the plane of the carbonyl group.
The positive charge on the carbonyl carbon atom means that it
is especially susceptible to attack by a nucleophile.
The negative charge on the carbonyl oxygen atom means that
nucleophilic addition is susceptible to acid catalysis.
Resonance structure of carbonyl group:
The carbonyl group is a polar group; therefore, aldehydes and ketones
have higher boiling points than hydrocarbons of the same molecular
weight. However, since aldehydes and ketones cannot have strong
hydrogen bonds between their molecules, they have lower boiling
points than the corresponding alcohols.
3.4 Nucleophilic Addition to the Carbon–Oxygen Double Bond
Aldehydes and ketones are especially susceptible to nucleophilic
addition because of the structural feature.
3.4.1 The Addition of Water
Geminal diols occur by addition of H2O to aldehydes and ketones.
3.4.2 The Addition of Alcohols
Aldehydes and ketones react with alcohols to form hemiacetals and
acetals by an equilibrium reaction.
Hemiacetal
RO
C O + 2ROH C OR
Acetal
3.4.3 The Addition of Hydrogen Cyanide and Sodium bisulfide
Hydrogen cyanide adds to the carbonyl groups of aldehydes and most
ketones to form compounds called cyanohydrins. (Ketones in which the
carbonyl group is highly hindered do not undergo this reaction).
3.4.4 The Addition of Strong Nucleophile
When the reagent is a strong nucleophile (Nu:-), addition usually takes
place in the following way, converting the trigonal planar aldehyde or
ketone into a tetrahedral product. In the second step, the oxygen
atom accepts a proton. This happens because the oxygen atom is now
much more basic; it carries a full negative charge as an alkoxide anion.
3.4.5 The Addition of Primary and Secondary Amines
Aldehydes and ketones react with primary amines to form imines and
with secondary amines to form enamines.
3.5 Oxidation and Reduction of Carbonyl Compounds
Aldehydes are much more easily oxidized than ketones. Aldehydes are
readily oxidized by strong oxidizing agents such as potassium
permanganate, and they are oxidized by such mild oxidizing agents as
silver oxide.
The ease with which aldehydes undergo oxidation differentiates them
from most ketones. Mixing aqueous silver nitrate with aqueous
ammonia produces a solution known as Tollens’ reagent. The reagent
contains the diamminosilver(I) ion, Ag(NH3)2+. Although this ion is a
very weak oxidizing agent, it oxidizes aldehydes to carboxylate anions.
As it does this, silver is reduced from the +1 oxidation state [of
Ag(NH3)2+] to metallic silver. Tollens’ reagent gives a negative result
with all ketones.
Metallic silver
Fehling reagent;
red precipitates
The carbonyl group of a ketone or an aldehyde can be reduced to a C-
OH group with catalytic hydrogenations. However, the carbonyl group
of a ketone or an aldehyde can be reduced to a CH2 group. One general
method—called the Clemmensen reduction—consists of refluxing the
ketone with hydrochloric acid containing amalgamated zinc.
Pd
RCHO + H2 RCH2OH
Zn, Hg / conc.HCl
RCHO RCH3
3.6 Keto-Enol Tautomerization
The keto and enol forms of carbonyl compounds are constitutional
isomers, but of a special type. Interconvertible keto and enol forms
are called tautomers, and their interconversion is called
tautomerization. Keto–enol tautomers are not resonance structures.
They are constitutional isomers in equilibrium (generally favoring the
keto form).
H O OH
C C C C
Keto- Enol-
3.7 α-Hydrogen Acidity of Carbonyl Compounds; Enolate Anion
α-hydrogens of carbonyl compounds can be removed by base. A base
catalyzes the formation of an enol through the intermediate
formation of an enolate anion.
O H B- O H
O H
C C + H-B
C C C C
stable anion
3.8 Aldol Condensation
An aldol reaction begins with addition of an enolate or enol to the
carbonyl group of an aldehyde or ketone, leading to a β-hydroxy
aldehyde or ketone as the initial product. An aldol addition is an
equilibrium reaction when it is conducted in a protic solvent with a base
such as hydroxide or an alkoxide. the initial aldol addition product
often dehydrates to form an α,β-unsaturated aldehyde or ketone.
When this is the result, the overall reaction is an aldol condensation.
O O OH O O
HO-,H2O
RCH2-C-H + RCH2-C-H RCH2-CH-CH-C-H RCH2-CH=C-C-H
-H2O
R R
Aldol product
3.9 Crossed Aldol Condensations
An aldol reaction that starts with two different carbonyl compounds
is called a crossed aldol reaction. Unless specific conditions are
involved, a crossed aldol reaction can lead to a mixture of products
from various pairings of the carbonyl reactants. Crossed aldol
reactions are possible with weak bases such as hydroxide or an
alkoxide when one carbonyl reactant does not have a hydrogen. A
reactant without a hydrogen cannot self-condense because it cannot
form an enolate.
O O O
HO O
HO-,H2O
RCH2-C-H + H-C-H CH2-CH-C-H H2C=C-C-H
-H2O
R R
