CHAPTER 9

ALDEHYDES AND KETONES

 Teaching Objectives and Requirements
 Understand: The Carbonyl Group, Physic
al Properties, Protecting Groups. Grasp:
Nomenclature, Reactions: Redox, Additio
n, Acetals and Ketals, Addition of Nitrogen
Compounds, The Aldol Condensation.
 Key points and Main Areas of Difficulty
 Reactions: Redox, Addition, Acetals and
Ketals, Addition of Nitrogen Compounds,
The Aldol Condensation.
 9.1 The Carbonyl Group
 A carbonyl group:functional group
 C and O atoms linked by a double bond
 Formaldehyde,CH2O,the simplest one

Nonbonding electron Nonbonding electron

pairs are shown. pairs are not shown.
.. O
O:
H C H C H
H representations
 sp2-hybridized, of formaldehyde
3σbonds , 120°, a πbond
 9.1 The Carbonyl Group
 Oxygen is more electronegative than
carbon.
 The oxygen atom attracts the
electrons in the carbon-oxygen double
bond.
 This makes the carbonyl bond polar.
..δ- .. -
O: :O :
+
Cδ C
(1) (2)
 9.1 The Carbonyl Group
 Carbonyl Compounds
 Aldehyde:bonded to at least one H atom.
O
R C H R could be alkyl,aryl groups and H(formaldehyde).
 Ketone:bonded to two other carbon atoms of eith
er alkyl or aryl groups.
O
R C R R could be alkyl, aryl groups.
 Aldehyde:the condensed formula RCHO or ArCH
O
 9.1 The Carbonyl Group
 Ketone:the condensed formula RCOR.
9.2 Nomenclature of Aldehydes and
Ketones
 Common names:for aldehyde and ketones with
low molecular weights.
O O O
H C H CH3 C H CH3 C CH3
formaldehyde acetaldehyde acetone
O O O
C H C CH3 C

benzaldehyde acetophenone benzophenone

CH3 CH3 O O

 ionone jasmone
9.2 Nomenclature of Aldehydes and
Ketones
 IUPAC Names of Aldehydes
 The final –e of the parent hydrocarbon is re
placed by the ending –al .
 The parent chain is numbered so that the c
arbonyl carbon atom is C-1.
CH3CH2CHCH3 2-methylbutane
CH3
4 3 2 1
CH3CH2CHCHO 2-methylbutanal
CH3
9.2 Nomenclature of Aldehydes and
Ketones
 The name of each substituent.
 The number of the carbon atom to which
it is attached.
 Added to the parent names as a prefix.
CH3 O
CH3 CH
3
CH C1 H
4 2
CH3
This is 2,3-dimethylbutanal,not 2,3-dimethyl-1-butanal.
9.2 Nomenclature of Aldehydes and
Ketones
 –CHO group has a higher priority than alk
yl,halogen,hydroxyl, and alkoxy groups.
 The names and positions of these groups
are indicated as prefixes.
OH O
2
CH3 CH CH C H This is 3-hydroxy-2-methylbutanal.
3
CH 13
 –CHO group has a higher priority than do
uble or triple bonds.
9.2 Nomenclature of Aldehydes and
Ketones
 The final –e of the name of the parent alke
ne or alkyne --- the suffix –al.
 The position of the multiple bond is indicat
ed by a prefix.
CH3 O
CH3 CH C C C H This is 4-methyl-2-pentynal.
5 4 3 2 1

 Containing other groups with a higher prio

rity, such as carboxylic acids, COOH
9.2 Nomenclature of Aldehydes and
Ketones
 The carbonyl group is given the prefix ox
o-.
 The position of the oxo group is given by a
number.
 The priority order is carboxylic acid > alde
hyde >ketone.
O O
2
CH3 C CH C H This is 2-methyl-3-oxobutanal
4 3 1
CH3
9.2 Nomenclature of Aldehydes and
Ketones
 The suffix carbaldehyde ---- an aldehyde group
attached to a ring.

CHO OHC

Br
cyclohexanecarbaldehyde cis-2-bromocyclopentanecarbaldehyde
 IUPAC Names of Ketones
 The carbonyl carbon atom has the lower numbe
r.
9.2 Nomenclature of Aldehydes and
Ketones
 This number appears as a prefix to the p
arent name.
 The identity and location of substituents a
re indicated with a prefix.
CH3 O
CH3 CH CH2 C CH3
5 4 3 2 1
This is 4-methyl-2-pentanone,not 2-methyl-4-pentanone

 Cyclic ketones are named as cyclo- alkan

ones.
9.2 Nomenclature of Aldehydes and
Ketones
 The carbonyl carbon atom receives the nu
mber 1.
 Gives the lower number to the first substit
uent encountered.
1 O O
Br
2 1
2
3
CH3
3-methylcyclohexanone 2-bromocyclopentanone
9.2 Nomenclature of Aldehydes and
Ketones
 X-, the HO-,RO- ,and multiple bonds have lo
wer priorities than the ketones group.
 A substituted ketone is named by the method
described previously for aldehydes.
9.3 Physical Properties of Aldehydes
and Ketones
 Oxygen is more electronegative than carb
on.
 The carbonyl group is polar.
-
H ¦Ä+ δ
.. H + .. -
C O: .. :
C O
CH3CH2 CH3CH2

 Boiling Points
 Have higher boiling points than the alkane
s of similar molecular weight .
9.3 Physical Properties of Aldehydes
and Ketones
 The bigger dipole-dipole intermolecular force
s due to the carbonyl group.
 Alcohols have smaller dipole moments than
carbonyl compounds.
 Hower,alcohols have higher boiling points th
an aldehydes and ketones.
 This is the result of hydrogen bonding in alco
hols.
 Not possible in carbonyl compounds.
9.3 Physical Properties of Aldehydes
and Ketones
 Solubility
 Aldehydes and ketones cannot form hyd
rogen bonds with one another.
 They cannot function as hydrogen bond
donors.
 However,the carbonyl oxygen atom has l
one pair electrons.
 They can serve as hydrogen bond accep
tors.
9.3 Physical Properties of Aldehydes
and Ketones
 This carbonyl groups can form hydrogen b
onds with water.
 Formaldehyde,acetaldehyde,and acetone
are soluble in water in all proportions.
:O : :O :
The lone pair electrons of the
H H H H
carbonyl oxygen atom serve as
:O : a hydrogen bond acceptor.
C
CH3 CH3
9.3 Physical Properties of Aldehydes
and Ketones
 The chain length increase.
 The solubility of carbonyl compounds in
water decrease.
 Their solubilities become more like those
of hydrocarbons.
 Both acetone and 2-butanone are excell
ent solvents.
 For polar organic compounds.
9.4 Redox Reactions of Carbonyl Co
mpounds
 C=O is in an oxidation state between that o
f an alcohol and a carboxylic acid.
 Thus,a carbonyl group can be reduced to a
n alcohol or oxidized to a carboxylic acid.
OH O O
reduction oxidation
C H C C OH

 Oxidation Reactions
 Tollens’s reagent is a basic solution of a sil
ver ammonia complex ion.
 9.4 Redox Reactions of Carbonyl Co
mpounds
 Tollens’s reagent is added to a tube cont
aining aldehyde solution.
 The aldehyde is oxidized to carboxylic a
cid.
 Metallic siver is deposited as a mirror on
the wall of the test tube.
O O
+ -
R C H + 2Ag(NH3)2 + 3 OH- R C O + 2Ag(s) + 2H2O + 2 NH3
9.4 Redox Reactions of Carbonyl Co
mpounds
 Fehling’s solution contains cupric ion,
Cu2+,as a complex ion in a basic solution.
 It oxidizes aldehyde to carboxylic acids
as the Cu2+ is reduced to Cu+.
 Forms a brick-red precipitate,Cu2O

O O
2+ - -
R C H + Cu + 5 OH
2 R C O + Cu2O(s) + 3 H2O
blue red
solution precipitate
9.4 Redox Reactions of Carbonyl Co
mpounds
 Blue color of Cu2+ fades as the red preci
pitate of Cu2O forms.
 Tollens’s reagent and Fehling’s solution
are mild oxidizing reagents.
 Neither of them oxidizes ketones.
 These reagents can be used to distingui
sh aldehydes from ketones.
 Reduction to Alcohols
9.4 Redox Reactions of Carbonyl Co
mpounds
 Lithium aluminum hydride,LiAlH4
 Sodium borohydride,NaBH4
 May be used to reduce a carbonyl group
.
 Cann’t reduced carbon-carbon multiple b
onds.
 Both reagents can offer negative hydrog
en ion.
9.4 Redox Reactions of Carbonyl Co
mpounds
O
C H CH2OH
NaBH4
CH3CH2OH

O OH
1.LiAlH4
C CH3 CH CH3
2. H3O+

O
C H CH2OH The catalysts can be nickel,
H2 palladium,or platinum.
catalysts
9.4 Redox Reactions of Carbonyl Co
mpounds
 Reduction to a Methylene Group
 A carbonyl group can be reduced directl
y to a methylene group.
 The Clemmensen reduction uses a zinc
amalgam(Zn/Hg) and HCl.
 The Wolff-Kishner reduction uses hydraz
ine (NH2NH2) and base.
9.4 Redox Reactions of Carbonyl Co
mpounds
O
C CH3
H Zn/Hg
HCl
cyclohexane carbaldehyde methylcyclohexane
O
C CH2CH3
H NH2NH2
KOH
actophenone ethylbenzene
9.5 Additon Reactiona of carbonyl C
ompounds
 Aldehydes and ketones contain a πbond
that undergoes addition reactions.
 The carbonyl bond is polar.
 O atom with partial - charge,C atom with
partial + charge.
 An unsymmetrical reagent can be seper
ated in two parts.
 The electrophilic part(+ charge) and the
nucleophilic part(- charge).
9.5 Additon Reactiona of carbonyl C
ompounds
 The electrophilic part(positive) bonds to t
he carbonyl oxygen atom(negative).
 The nucleophilic part(negative) bonds to
the carbonyl carbon atom(positive).
+ -
¦Ä δ..
Nucleophiles C O: Electrophiles
attack here. attacks here.
9.5 Additon Reactiona of carbonyl C
ompounds
 Relative Reactivities of Aldehydes and ket
ones
 Nucleophiles react faster with aldehyde than
with ketones.
 Electronic and steric effects.
 A ketone has two alkyl groups attached to the
carbonyl carbon atom.
 Alkyl groups donate electron density to the car
bonyl carbon atom.
 Stablize its partial positive charge.
9.5 Additon Reactiona of carbonyl C
ompounds
 At least one H atom is attached to the ca
rbonyl C atom of aldehyde.
 Less electron density is donated to parti
al positive C=O carbon atom.
 The C=O carbon atom of an aldehyde h
as a larger partial positive charge.
 As a consequence,nucleophiles react fa
ster with aldehydes than with ketones.
9.5 Additon Reactiona of carbonyl C
ompounds
.. - .. -
:Oδ :Oδ
C¦Ä+ C¦Ä+
R H R R
less stablization more stablization
more reactive less reactive

 The sizes of groups also affect the reactivi

ty of aldehydes and ketones.
 Two alkyl groups of a ketone are more ste
rically hindered.
 An aldehyde has only a hydrogen atom a
nd alkyl group.
9.5 Additon Reactiona of carbonyl C
ompounds
 Thus,a nuleophile can approach the C=
O group of an aldehyde more readily.
 The reaction occurs faster with an aldeh
yde.
 These rules lie in all aldehyde and keto
ne compounds.

H3C O CH3 O
H3C C C C CH3 slower CH3 C CH3 faster
H3C CH3
9.6 Synthesis of Alcohols from C
arbonyl Compounds
 Grignard reagents are used to form carbo
n-carbon bonds.
 Contain a very strongly polarized carbon-
magnesium bond.
 The C atom has a partial negative charge.
-
Mg δ ¦Ä+
R X ether R MgX C MgX
9.6 Synthesis of Alcohols from C
arbonyl Compounds
 The carbon atom of the Grignard reagen
t resembles a carbanion.
 It reacts as a nucleophile and adds to th
e electrophilic C atom of a C=O group.
C MgX

.. ether .. H2O ..
R MgX + C O: R C O
.. Mg .. H + HOMgX
R C O

a magnesium
alkoxide
9.6 Synthesis of Alcohols from Carbo
nyl Compounds
 A Grignard reagent adds to various types
of carbonyl compounds.
 Give primary, secondary, and tertiary alco
hols.
H H
H .. ether .. H2O ..
R MgX + C O: R C O .. Mg R C O .. H + HOMgX
H H H
a magnesium a primary alcohol
alkoxide
H [Link]
MgCl + C O 2. CH2OH
H H2O
9.6 Synthesis of Alcohols from Carbo
nyl Compounds

H H
H .. ether .. H2O 1 ..
1 1
R MgX + C O: R C O .. Mg R C O .. H + HOMgX
R R R
a magnesium a secdonary alcohol
alkoxide
[Link]
CH3 MgBr + C H 2. CH CH3
H2O
O OH
 9.6 Synthesis of Alcohols from Carbo
nyl Compounds

R R
R .. ether .. H2O 1 ..
1 1
R MgX + C O: R C O .. Mg R C O .. H + HOMgX
R R R
a magnesium a tertiary alcohol
alkoxide
OH
[Link]
CH3CH2 MgBr + CH3CH2CH2CCH3 CH3CH2CH2CCH3
2.H2O
O CH2CH3
9.6 Synthesis of Alcohols from Carbo
nyl Compounds
 Acetylenic Alcohols
 Alkynide ions, the conjugate bases of alky
nes.
 With negative charge on carbon (carbanio
n,nucleophile).

R C C

 React with carbonyl groups in much the sa

me way as Grignard reagents do.
9.6 Synthesis of Alcohols from Carbo
nyl Compounds
 The alkynides are prepared in an acid-bas
e reaction.
 Acetylene or a terminal alkyne react with s
odium amide in ammonia.
NH3
H C C H + NaNH2 H C C Na + NH3
O OH
1.NH3
+ H C C Na C C H
2. H3O+
1-ethynylcyclohexanol
9.7 Addition of Oxygen Compounds
 The nucleophilic oxygen atom of both wate
r and alcohols:lone pair electrons.

H O H R O H
 Addition of water ＜＝＝＝＞ a hydrate.
 Addition of an alcohol ＜＝＝＝＞ a hem
iacetal or hemiketal.
 The water and alcohols are weak nucleoph
iles.
9.7 Addition of Oxygen Compound
s
 Each of these reactions is reversible.
 Addition of Water OH
H H
O
H O + C H C OH
H
H
formaldehyde hydrate
 Water adds to aldehydes and ketones to form
hydrates.
 The proton of water to the oxygen atom.
 The hydroxide ion to the carbon atom.
9.7 Addition of Oxygen Compound
s
 Other aldehydes are substantially less hy
drated.
 Ketones are hydrated to an even smaller
extent, usually less than 1%.
 The hydrates of aldehydes and ketones u
sually cannot be isolated.
 The large amount of water forces the equil
ibrium position to the right.
9.7 Addition of Oxygen Compound
s
 Addition of Alcohols
 It is an acid-catalyzed reaction, which doe
s not occur in basic or neutral solution.
 The hydrogen atom of the alcohol adds to
the carbonyl oxygen atom.
 The –OR′ portion (alkoxy group) adds to t
he carbon atom.
9.7 Addition of Oxygen Compound
s
H R' O
H
C O
R' O + C O H
R H
R
hemiacetal

H R' O
R
R' + C O C O H
O R
R R
hemiketal
9.7 Addition of Oxygen Compound
s
 If the carbonyl compound is an Aldehyde
Hemiacetal
 a Ketone Hemiketal
 Hemiacetals and hemiketals are usually un
stable compounds.
 The equilibrium position for the preceeding
reactions lies to the left.
 Cyclization is favorable because the two f
unctional groups are close to each other.
9.7 Addition of Oxygen Compound
s

The ring oxygen atom is

derived from the hydroxyl group.

OH O OH
CHO C
H

The carbon atom is derived from

the carbonyl group.
9.7 Addition of Oxygen Compound
s
 Mechanism of Addition of Alcohols
 ①Acid-catalyzed addition of an alcohol to a
n aldehyde or ketone.
 Protonation of the carbonyl oxygen atom
(an electron pair donor, or Lewis base).

[ ]
H H
H +
O H + C O H C O H
C
R R R

trigonal planar resonance stabilized

carbonyl compound oxocarbocation
9.7 Addition of Oxygen Compound
s
 Produce a resonance-stabilized carbocat
ion.
 ②Reacts with the lone pair electrons of the
oxygen atom of the alcohol R’―OH.
H
H R' O
H
R' O C O H
C O H
R H
R
conjugate acid of
a hemiacetal
9.7 Addition of Oxygen Compound
s
 A proton is transferred from the conjugate
acid of the hemiacetal.
 The proton becomes available again for th
e first step of the reaction sequence.
 Thus, the reaction is acid catalyzed again.
9.8 Formation of Acetals and Ketals
 The –OH group in either a hemiacetal or a hemi
ketal can be replaced by -OR′.
 This reaction is reversible.
 Occurs readily in acidic solution.
 Two alkoxy groups attached to the same carb
on atom.
 An acetal:a hydrogen atom and an alkyl grou
p attached to the carbon atom.
 The ketal:two alkyl groups attached.
9.8 Formation of Acetals and Ketals
H R' O R' O
H+
R' O C O H C O R' H2O
H H
R R
hemiacetal acetal

H R' O + R' O
H
R' O C O H C O R' H2O
R R
R R
hemiacetal ketal
 9.8 Formation of Acetals and Ketals

 Two molar equivalents of alcohol

 Per mole of the original carbonyl compoun
d.
H H CH3 O
+
H
2CH3 O C O C O CH3
H H2O
CH3CH2CH2
CH3CH2CH2

 Cyclic hemiacetals or hemiketals produce

cyclic acetals or ketals.
9.8 Formation of Acetals and Ketals
OH O OH O OCH3
H+ CH3OH
CHO C C H 2O
+
H H H
cyclic hemiacetal cyclic acetal

 Reactivity of Acetals and Ketals

 The conversion are reversible in acid solution.
 The position of the equilibrium can be shifted.
 Removing the water formed in the reaction
 Increasing the concentration of the alcohol.
9.8 Formation of Acetals and Ketals
hemiacetal alcohol acetal water

Adding alcohol "pushes" Removing water "pulls"

equilibrium to the right. equilibrium to the right.

 The acid-catalyzed hydrolysis of acetals or

ketals, is favored when water is added.
 However, acetals and ketals do not react i
n neutral or basic solution.
 Protection of aldehydes or ketones
9.9 Addition of Nitrogen Compou
nds
 Nucleophiles:contain nitrogen
 Ammonia, NH3, and amines of the general
formula RNH2.
 Imines:the carbonyl carbon atom bonded t
o the nitrogen atom by a double bond.
 Addition-elimination reaction.

[
H

]
H
G N C O G N C N H2O
C O H G
H
9.10 Reactivity of the α- Carbon Ato
m
 The α- carbon atom
O H  hydrogen atom

C C C

 carbon atoms

 Acidity of α-Hydrogen Atoms

 Partial positive charge
 Attracts electrons in neighboring bonds by
an inductive effect.
9.10 Reactivity of the α- Carbon Ato
m
 The α-carbon atom loses electron density
and acquires a partial positive charge.
 A α-hydrogen atom is more acidic.
 An enolate anion, stabilized by resonanc
e. O O
H H
C C C C
H CH3 H CH3
contributing resonance
structures of enolate ion
9.10 Reactivity of the α- Carbon Ato
m
 One contributing resonance structure: a neg
ative charge on the oxygen atom.
 The other:a negative charge on the carbon
atom.
 The charge on the enolate anion is delocaliz
ed.
 It is more stable than a carbanion,in which n
o such resonance stabilization is possible.
9.10 Reactivity of the α- Carbon Ato
m
H O H O
C C C C
H CH3 H CH3
contributing resonance
structures of enolate ion
 Keto-Enol Equilibria
 Both aldehydes and ketones exist as an eq
uilibrium mixture.
 The keto and the enol forms
9.10 Reactivity of the α- Carbon Ato
m
 Isomeric compounds
 Simple aldehydes and ketones exist predo
minantly in the keto form.
 Acetone has less than 0.01% of the enol f
orm.
H O H O H
C C C C
H CH3 H CH3
H
acetone acetone
(keto form) (enol form)
9.10 Reactivity of the α- Carbon Ato
m
 This type of isomerism is called tautomeri
sm.
 The two isomeric forms are called tautom
ers.
 9.11 The Aldol Condensation
 Two carbonyl compounds can react with o
ne another.
 Give a condensation product that is both a
n aldehyde and an alcohol.
O O -
OH O
OH
R CH2 C H CH2 C H R CH2 CH CH C H
R R
an aldol

 A new carbon-carbon bond is formed.

9.11 The Aldol Condensation
 Mechanism
 Step 1: one aldehyde molecule to give a n
ucleophilic enolate anion.
H O H O
HO C C H2O
C C
H
H H H H
enolate anion
9.11 The Aldol Condensation
 Step 2:Reacts with the carbonyl carbon at
om of another aldehyde molecule.
 The product is the alkoxide anion of an ald
ol.
H O H O O O
C C C C CH3 C CH2 C
H H H H
H H H
nucleophile
9.11 The Aldol Condensation
 Step 3: a proton from water combines with
the alkoxide anion.
 Regenerates a hydroxide anion to cycle.

H O O OH O
H O CH3 C CH2 C CH3 C CH2 C H O
H H H H
 9.11 The Aldol Condensation
 Dehydrate to give a double bond in conjug
ation with the carbonyl group.
 Dehydration of the aldol shown followed b
y reduction gives 1-butanol.

OH O O
H+ H2
CH3CH2CH2CH2OH
CH3 C CH2 C CH3 CH CH C
-H2O Ni
H H H
9.11 The Aldol Condensation
 Mixed Aldol Condensation
 Two different aldehydes are mixed in a ba
sic solution.
 A dreadful mixture is produced.
 One of the aldehydes dose not have any
α-hydrogen atoms.
 One of the aldehydes is less reactive towa
rd nucleophiles than the other.
9.11 The Aldol Condensation

O O OH O
C OH- C CH2 C
CH3 C
H H H H

OH O O
C CH2 C -H2O CH CH C
H H H
cinnamaldehyde