Chapter 13

Aldehydes and Ketones 

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 The Carbonyl Group
• In this and several following chapters, we study 
the physical and chemical properties of classes 
of compounds containing the carbonyl group 
•             

                 C=O
• aldehydes and ketones (Chapter 13)
• carboxylic acids (Chapter 14)
• acid halides, acid anhydrides, esters, amides (Chapter 15)
• enolate anions (Chapter 16)

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 Structure
• the functional group of an aldehyde is a carbonyl group 
bonded to a H atom  
• the functional group of a ketone is a carbonyl group 
bonded to two carbon atoms
O O O
HCH CH3 CH CH3 CCH3
Methanal Ethanal Propanone
(Formaldehyde) (Acetaldehyde) (Acetone)

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 Aldehydes and Ketones

 In an aldehyde, an H atom is attached to a carbonyl group
         O carbonyl group
                              
   CH3­C­H
 In a ketone, two carbon groups are attached to a carbonyl 
group
         O carbonyl group
                              
   CH3­C­CH3

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 Naming Aldehydes

 IUP AC Rep lace t he -e in the alkane name -al

 Common Add aldehyde to the prefixes for m ( 1C),
acet (2C), pr opi on(3), and butr y(4C)

    O                     O    O

                                
H­C­H   CH3­C­H CH3CH2C­H
  methanal   ethanal    propanal
  (formaldehyde) (acetaldehyde)  (propionaldehyde)

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 Aldehydes as Flavorings

O O
CH O
CH
CH=CH CH

HO
OCH3

Benzaldehyde Vanillin Cinnamaldehyde

(almonds) (vanilla beans) (cinnamon)

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 Aldehydes: Common Examples
O
methanal (formaldehyde) H O
H H
C
O
ethanal (acetaldehyde)
H H C OH
O
propanal (propionaldehyde)
HO C H
H H C OH
O
butanal (butyraldehyde) H C OH
H
CH2OH
O
2-methylpropanal (isobutyraldehyde) glucose
H
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 Naming Ketones

 In t he IUP AC name, the -e in the alk ane n ame is

rep lac ed w it h -one
 In t he com mon name, add t he wor d ketone aft er
naming the alk yl gr oups at tached to the carb onyl
gro up
        O
                     O  O
                                 
CH3 ­C­CH3     CH3­C­CH2­CH3
Propanone 2-Butanone
(Dimethyl ketone) ( Ethyl me thy l ketone)

Cyclohexanone

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 Ketones: common examples

CH 2OH
        O O
        
Butter flavor CH3­C­C­CH3  C O
Butanedione HO C H
H C OH
                            O
                           H C OH
Clove flavor CH3­C­CH2CH2CH2CH2CH3
2-heptanone CH2OH
D-Fructose

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 Ketones as Hormones

CH2OH
CH3 O
O
OH
CH3

Cortisone
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 Nomenclature
• IUPAC names:
• the parent chain is the longest chain that contains the 
carbonyl group

• for an aldehyde, change the suffix from ­e to ­ al
• for an unsaturated aldehyde, show the carbon­carbon 
double bond by changing the infix from ­an­ to 
­an­ ­en­; the 
­en­
location of the suffix determines the numbering pattern
• for a cyclic molecule with –CHO bonded to the ring, 

   use suffix ­carbaldehyde

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 Nomenclature
O O O
3 1 1 7 5 3 1
3 H
4 2 H 2 8 H
6 4 2
3­Methylbutanal 2­Propenal (2E)­3,7­Dimethyl­2,6­octadienal
(Acrolein) (Geranial)

CHO HO 4 1 CHO
Cyclopentane­ trans­4­Hydroxycyclo­
carbaldehyde hexanecarbaldehyde

O O O
O

5­Methyl­3­ 2­Methyl­    Acetophenone Benzophenone

hexanone cyclohexanone
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 Nomenclature
Functional  Example of When the Functional
Group Suffix Prefix Group Has a Lower Priority
Carboxyl ­oic acid O
oxo­ COOH
Aldehyde ­al 3­Oxopropanoic acid H
O
Ketone ­one oxo­ 3­Oxobutanoic acid COOH

Alcohol ­ol hydroxy­ 4­Hydroxybutanoic acid HO COOH

NH2
Amino ­amine amino­ 3­Aminobutanoic acid COOH

Sulfhydryl ­thiol mercapto­ 2­Mercaptoethanol HS

OH

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 Nomenclature
• Common names
• for an aldehyde, the common name is derived from the 
common name of the corresponding carboxylic acid
• for a ketone, name the two alkyl or aryl groups bonded 
to the carbonyl carbon and add the word ketone
O O O O
H H H OH H OH
Formaldehyde Formic acid Acetaldehyde Acetic acid

O
O O

Ethyl isopropyl ketone Diethyl ketone Dicyclohexyl ketone

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 Physical Properties
• Oxygen is more electronegative than carbon (3.5 
vs 2.5) and, therefore, a C=O group is polar
δ+ δ- +
O: O: –

:
C O C C

:
More important
  Polarity of a contributing
carbonyl group structure

• aldehydes /ketones are polar compounds 
                                               (interact by dipole­dipole interactions)
• they have higher boiling points 
• more soluble in water than nonpolar compounds of 
comparable molecular weight

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 Reactions
• The most common reaction theme of a carbonyl 
group is addition of a nucleophile to form a 
tetrahedral carbonyl addition compound

: O:

:
-
R
Nu: - + C O: Nu C
:

R R
R
Tetrahedral carbonyl
 addition compound

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    8. Formation of Oximes/ Hydrazones
• Grignard Reaction
Reactions
• Hemiacetal Formation
: O:

:
-
• Imine Formation R
Nu: - + C O: Nu C
• Reductive Amination

:
R R
R
Keto­enol Tautomerism Tetrahedral carbonyl
•  addition compound
• Alpha­halogenation
• Oxidation/ Reduction
• Oximes & Hydrazones

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    1. Grignard Reagents
• Grignard reagents  RMgX 
    where R is an alkl or aryl group and X is a halogen

     Given the difference in electronegativity between carbon and magnesium 
(2.5 ­ 1.3), the C­Mg bond is polar covalent, 
     with Cδ­ and Mgδ+

Br ether MgBr
+ Mg
1­Bromobutane Butylmagnesium bromide

ether
Br + Mg MgBr
Bromobenzene Phenylmagnesium bromide

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    2. Hemiacetal Formation
• Hemiacetal: a molecule containing an ­OH goup 
and an ­OR group bonded to the same carbon
O H OH
H+
CH3CCH3 + OCH2CH3 CH3 C-OCH2 CH3
CH3
A hemiacetal

• hemiacetals are minor components of an equilibrium 
mixture except where a 5­ or 6­membered ring can form
3 2
O redraw to show H 3 2
5 3
4 2 the OH close to 5 4 4
1 H 1 O 5
the CHO group O O 1 OH
OH H
4­Hydroxypentanal   A cyclic hemiacetal
(major form present
     at equilibrium)

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    2. Hemiacetal Formation
• Acetal: a molecule containing two ­OR groups 
bonded to the same carbon
OH OCH2CH3
+
H
CH3C-OCH2CH3 + CH3CH2OH CH3 C-OCH2CH3 + H2 O
CH3 CH3
A hemiacetal A diethyl acetal

O
H CH3 OH
O OH + H2 O
OH +
H O OCH3

4­Hydroxypentanal A cy clic acetal

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     2. Acetal Formation
1. Proton transfer from HA to the hemiacetal oxygen
+
H H
HO O
-
R-C-OCH3 + H A R-C-OCH3 + A
H H
An oxonium ion
2. Loss of H2O gives a cation
+
H H
O
+ +
R-C-OCH3 R-C OCH3 R-C OCH3 + H2O
H H H
A resonance­stabilized cation

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    2. Acetal Formation
3. reaction of the cation (an electrophile) with an alcohol 
(a nucleophile)
+
H H O CH3
+
CH3-O + R-C OCH3 R-C-OCH3
H H
A protonated acetal
4. proton transfer to A­ gives the acetal and regenerates 
the acid catalyst
+
H O CH3 O CH3
A + R-C-OCH3 HA + R-C-OCH3
H
H
A protonated acetal An acetal
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    2. Acetal Formation
• Draw a structural formula for the acetal formed in 
each reaction
OH H2 SO4
(a) O + HO
Ethylene
glycol

OH O H2 SO4
(b) +
OH

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    2. Acetal Formation
Acetals as Protecting Groups
• one way to synthesize the ketoalcohol on the right is 
by a Grignard reaction
O
O OH O
Ph H Br ??
+ H Ph H
Benzaldehyde 4­Bromobutanal 5­Hydroxy­5­phenylpentanal

• but first the aldehyde of the bromoaldehyde must be 
protected; one possibility is as a cyclic acetal
O + O
Br OH H
Br
H + HO O + H2O
Ethylene glycol A cyclic acetal

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    3. Imine Formation
• Imine: a compound containing a C=N bond; also 
called a Schiff base
• formed by the reaction of an aldehyde or ketone with 
ammonia or a 1° amine
+
H
O + NH3 NH + H2O
Cyclohexanone Ammonia An imine

O +
H
CH3CH + H2N CH3 CH=N + H2 O

Ethanal Aniline An imine

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    3. Imine Formation
1. addition of the amine to the carbonyl carbon followed 
by proton transfer 

O O­ H O
H
+
C + H2N-R C N-R C N-R
H H
A tetrahedral carbonyl
addition intermediate

2. two proton­transfer reactions and loss of H2O
+
H H H
H O O H
+
O H + C N-R C N-R C N-R + H2 O + H O H
H H H H
O   An imine

H
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Imine (Schiff's Base) Formation

•• ••
H2N • + C O• HN C O H
•• ••
• •
R R
a carbinolamine

••
N C (imine) + H2O
R
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Example

  O

CH + CH3NH2

CH=NCH3 + H2O
N-Benzylidenemethylamine (70%)

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Example

  O

CH + CH3NH2   OH

CH
  NHCH3
CH=NCH3 + H2O

N-Benzylidenemethylamine (70%)
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Example

O + (CH3)2CHCH2NH2

NCH2CH(CH3)2 + H2O

N-Cyclohexylideneisobutylamine
(79%)
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Example

O + (CH3)2CHCH2NH2
 
OH
NHCH2CH(CH3)2
 

NCH2CH(CH3)2 + H2O

N-Cyclohexylideneisobutylamine
(79%)
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 Rhodopsin

• reaction of vitamin A aldehyde (retinal) with an amino 
group on the protein opsin gives rhodopsin

11
12

+ H2N-Opsin

C=O
11­cis­Retinal H

C=N-Opsin
    Rhodopsin H
(Visual purple)

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    4. Reductive Amination
• Reductive amination: 
    the formation of an imine followed by its reduction to an amine

H+ H2 / Ni
O + H2N N
-H2O
Cyclohex­ Cyclohexyl­ An imine
anone amine (not isolated)
(a 1° amine)
H
N
Dicyclohexylamine
(a 2° amine)
• reductive amination is a valuable method for the conversion of ammonia 
to a 1° amine, and a 1° amine to a 2° amine

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    5. Keto­enol Tautomerism
• Enol: molecule with ­OH on a C=C of an alkene
O OH
CH3 -C-CH3 CH3 -C=CH2
Acetone Acetone
• the keto form  (keto form) (enol form)

predominates  % Enol at
Keto form Enol form Equilibrium
for most 
O OH
simple  CH3CH CH2=CH 6 x 10
­5

aldehydes and  O OH
ketones  CH3CCH3 CH3C=CH2 6 x 10­7
O OH
­5
4 x 10

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    5. Keto­enol Tautomerism
• Problem: draw two enol forms for each ketone
O
O
(a) (b)

• Problem: draw the keto form of each enol
O
CHOH OH OH
(a) (b) (c)
OH

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    5. Keto­enol Tautomerism
• Mechanism (acid catalysed)
1. proton transfer to the carbonyl oxygen
••
+ •• H
O O
•
•

fast
CH3-C-CH3 + H-A CH3-C-CH3 + A-

•
•
Keto form The conjugate acid
of the ketone

2. proton transfer from the α­carbon to A:­
+ •• H
••
O slow OH
•
•
CH3-C-CH2 -H + A
-
CH3-C=CH2 + H-A
•
•

Enol form

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    6. α­Halogenation

• Aldehydes and ketones with an α­hydrogen react 
with Br2 and Cl2 to give an α­haloaldehyde or an 
α­haloketone
O O
Br
CH3 COOH
+ Br2 + HBr

Acetophenone α­Bromoacetophenone

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    6. α­Halogenation
• the key intermediate in α­halogenation is an enol
1. formation of the enol
O OH
H+

Keto form Enol form

2. nucleophilic attack of the enol on the halogen
H
O O
Br
+ Br Br + H-Br

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    7. Oxidation­Reduction
• Aldehydes are one of the most easily oxidized of 
all functional groups
CHO H2 CrO4 COOH
Hexanal Hexanoic acid

MeO CHO MeO COOH

+ Ag2O THF, H2O HCl + Ag
HO NaOH H2 O HO
Vanillin Vanillic acid

2 CHO + O2 2 COOH
Benzaldehyde Benzoic acid

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    7. Oxidation­Reduction
• Ketones are not normally oxidized by H2CrO4; in 
fact this reagent is used to oxidize 2° alcohols to 
ketones
• they are oxidized by HNO3 at higher temperatures
• oxidation is via the enol
O OH O
HNO3 HO
OH
O
Cyclohexanone Cyclohexanone Hexanedioic acid
(keto form) (enol form) (Adipic acid)

• adipic acid is one of the starting materials for the 
synthesis of nylon 66  
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    7. Oxidation­Reduction
• aldehydes can be reduced to 1° alcohols
• ketones can be reduced to 2° alcohols
O
reduction R-CH2 OH
R-CH
An aldehyde A primary
alcohol

O OH
reduction
R-C-R' R-CH-R'
A ketone A secondary
alcohol

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    7. Oxidation­Reduction
• Catalytic reductions are generally carried out 
from 25° to 100°C and 1 to 5 atm H2
O OH
Pt
+ H2
25 oC, 2 atm
Cyclohexanone Cyclohexanol

O
2H2
• a carbon­carbon double bond may also be reduced 
H OH
Ni
under these conditions
  trans­2­Butenal 1­Butanol
(Crotonaldehyde)

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    7. Oxidation­Reduction
Metal Hydride Reductions
• The most common laboratory reagents for the 
reduction of aldehydes and ketones are NaBH4 
and LiAlH4 
• both reagents are sources of hydride ion, 
hydride ion H:­, a very 
strong nucleophile
H H
+ +
Na H-B-H Li H-Al-H H:
H H
   Sodium  Lithium aluminum Hydride ion
borohydride   hydride (LAH)  

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    7. Oxidation­Reduction

NaBH4 Reductions

• reductions with NaBH4 are most commonly carried out 
in aqueous methanol, in pure methanol, or in ethanol
• one mole of NaBH4 reduces four moles of aldehyde or 
ketone
O
4RCH + NaBH4 methanol

- + H2O
(RCH2O) 4B Na 4RCH2OH + borate 
A tetraalkyl borate salts

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    7. Oxidation­Reduction

NaBH4 Reductions

• the key step in metal hydride reductions is transfer of a 
hydride ion to the C=O group to form a tetrahedral 
carbonyl addition compound
+
H O O BH3 Na
+ H2O
Na H-B-H + R-C-R' R-C-R' from 
H H water
O-H
from the hydride 
reducing agent R-C-R'
H

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    7. Oxidation­Reduction
Metal Hydride Reductions

• metal hydride reducing agents do not normally reduce 
carbon­carbon double bonds, and selective reduction 
of C=O or C=C is often possible
O OH
1. NaBH4
RCH=CHCR' RCH=CHCHR'
2. H2 O

O O
Rh
RCH=CHCR' + H2 RCH2 CH2 CR'

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 Aldehydes can be prepared
by reduction.
• This would be desirable to do:
O O
[H]
R C Cl R C H

[H] represents any general reduction

• The problem is, how to stop the reduction at

the aldehyde state, without reducing all the
way to a primary alcohol?
WWU -- Chemistry

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 Among the most useful modified aluminum
hydride (LiAlH4) reducing agents is
Diisobutylaluminum Hydride, also known as
DIBALH.

CH3 H CH3

CH3 CH CH2 Al CH2 CH CH3

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 Nitriles can also be reduced to 
aldehydes, using DIBALH
DIBALH H 2O
C N
toluene HCl
-78°C

Benzaldehyde
(90% yield)

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    8. Formation of Oximes/ Hydrazones

R R
.. acid
C O + H2N OH C N OH + H2O
R R
an oxime

•Aldehydes and ketones react with hydroxylamine to

yield oximes.
•Oximes are important derivatives in qualitative organic
analysis.

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    8. Formation of Oximes/ Hydrazones

R R
.. acid
C O + H2N NH R C N NH R + H2 O
R R
a hydrazone

•Aldehydes and ketones react with substituted hydrazines

to yield substituted hydrazones.
•The equilibrium is generally unfavorable.
•Exception: when R is an aromatic ring.

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    8. Formation of Oximes/ Hydrazones
2,4­Dinitrophenylhydrazones
NO2
R
.. acid
C O + H2N NH NO2
R
2,4-DNP’s are the
most important NO2
of all derivatives R
for aldehydes
and ketones. C N NH NO2 + H2O
R

a 2,4-dinitrophenylhydrazone

a 2,4-DNP

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 Aldehydes and
Ketones

End Chapter 13
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