ALDEHYDES & KETONES

(ALKANALS & ALKANONES)

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 ALDEHYDES & KETONES (ALKANALS & ALKANONES)
: O: :O: : O:
R C H
Aldehydes & ketones both
R C R' C
ketone
contain the carbonyl group.
aldehyde
carbonyl group

 The simplest aldehyde is formaldehyde (CH2O). It is the only

aldehyde without an alkyl group attached to the carbonyl C.
: O: : O:
All other aldehydes, such as acetaldehyde
H C H (CH3CHO), have one alkyl group and one CH3 C H
formaldehyde H attached to the carbonyl C. acetaldehyde

 All ketones have two alkyl groups attached to the carbonyl C.

: O: : O: : O:

C C C
H3C CH3 H3C CH2CH3 CH3

dimethyl ketone methyl ethyl ketone methyl phenyl ketone

(acetone) (MEK) (acetophenone) 2
 Aldehydes and Ketones are Electrophiles
Nu:-
 The carbonyl group has a strong dipole. 
: O: 
EN(O-C) = (3.5-2.5) = 1.0 (a polar bond) +
C 
 The + carbon is an electron acceptor,
(an electrophile). E+

 Good nucleophiles (CH3MgBr) and even fair nucleophiles (NH3)

will readily add to the carbonyl group of aldehydes and ketones.
tetrahedral ..
alkoxide : O :
: O:
The weak  bond breaks as the
R C H R C R Nu:- adds, so that C remains
3
sp2 Nu: -
sp tetravalent ( 5 bonds).
Nu

 The alkyl group and the H atom bonded to the carbonyl are not leaving
groups. They are not displaced because hydride (H:-) and alkanides
(R:-) are extremely strong bases.
 pKb H:- = -21 and pKb :CH3- = -40! (:CH3- = methide).
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 Aldehydes and Ketones are Electrophiles
 Aldehydes and ketones are moderately reactive as electrophiles
(electron acceptors) among the carboxylic acid derivatives.
: O:
acid chloride ..
:O:
..
: O: R C .. :
Cl
most
R C ..
O C R acid anhydride
: O: reactive
: O: aldehyde
R C H
R C R ketone
:O:
: O: ester ..
.. R C O
.. R
R C OH
.. carboxylic acid :O:
.. H
amide R C N
H
R C N: :O: least
nitrile
.. _ reactive
carboxylate R C ..:
O
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 Basicity of Aldehydes and Ketones
-
Nu:
 The - oxygen is a weak base (pKb ca. 21) 
: O: 
Its non bonded e’s are protonated by strong acids.
+
C 
H
H
: O: + : O+ : O: E
+
H HSO4-
R C R R C R C R
R
+

 The + charge is shared with the carbonyl C by resonance

forming a carbocation – a very good E+.
 Even weak Nu:-’s (like H2O and ROH) will donate electrons to an
aldehyde or ketone in the presence of a strong acid catalyst,
e.g., H2SO4 or HCl.
H
H
: O: : O:
H +
HSO4- : O:
R C .. R C R
R R C R
+ CH3CH2OH
.. +
CH3CH2OH
..
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 Acidity of Aldehydes and Ketones
 The -carbon is the carbon bonded to the carbonyl, not the
carbonyl carbon itself.
 Hydrogens bonded to the carbonyl carbon, the -carbon, the
-carbon, etc. are not polar and thus are not acidic hydrogens.
-hydrogens
pKa = ca. 17 in aldehydes
H :O : pKa = ca. 19 in ketones
pKa = ca. 55 for H

-hydrogens in H C C C The carbonyl H of an
aldehydes H
and ketones aldehyde is not acidic.
H H It's pKa is ca. 50.

 The -hydrogens can be removed by strong bases because the

carbanion that forms is stabilized by resonance with the
adjacent carbonyl oxygen forming an enolate.
H :O : ..
H H H :O : H :O :
 H

H C C C H C C
.. C
H C C C
H OH- H
H
H
H H H enolate
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 Boiling Points and Solubility of Aldehydes and Ketones

 The carbonyl group is strongly polar but does not produce

hydrogen bonding (It has no polar hydrogens). As a result, the
boiling points of aldehydes and ketones are higher than the
nonpolar hydrocarbons and the alkyl halides but lower than
those of alcohols.
 Formaldehyde is a gas at room temperature (b.p. = -21 C) but
heavier aldehydes are liquids. Acetone, the simplest ketone, is
a liquid at room temperature (b.p. = 56 C).
 Lower molecular weight aldehydes and ketones are water
soluble. Acetone, formaldehyde and acetaldehyde are miscible
in water.

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 IUPAC Nomenclature of Aldehydes

Aldehydes: in open chains:

alkane+al  “alkanal”

O OH O O
CH3CHBrCH2C H CH3CHCH2CH2C H CH2C H
4 3 2 1 5 4 3 2 1 2 1
3-bromobutanal 4-hydroxypentanal 2-phenylethanal

 The parent chain must contain the CHO- group, and this group is
numbered as carbon 1 (because it is always at a chain end).

Aldehydes: attached to rings:

ring+carbaldehyde  “ringcarbaldehyde”

O O
HO CHO
C H C H

benzenecarbaldehyde 3-hydroxycyclopentanecarbaldehyde

cyclohexanecarbaldehyde
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 Functional Group Precedence in Nomenclature
Functional Group Name as Suffix Name as Prefix
Principal Groups
Carboxylic Acids -oic acid carboxy
–carboxylic acid
Acid Anhydrides -oic anhydride
-carboxylic anhydride
Esters -oate alkoxycarbonyl
-carboxylate
Acid Halides -oyl halide halocarbonyl
-carbonyl halide
Amides -amide amido
-carboxamide
Nitriles -nitrile cyano
-carbonitrile
Aldehydes -al oxo
-carbaldehyde
Ketones -one oxo
Alcohols -ol hydroxy
Phenols -ol hydroxy
Thiols -thiol mercapto
Amines -amine amino
Imines -imine imino
Alkenes -ene alkenyl
Alkynes -yne alkynyl
Alkanes -ane alkyl

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 Common Names of Aldehydes

 In the common system, aldehydes are named from the common

names of the corresponding carboxylic acid.
 The ‘ic acid’ ending is replaced with ‘aldehyde’.
Structure IUPAC name Common name Structure IUPAC Common name
HCO2H methanoic acid formic acid HCHO methanal formaldehyde
CH3CO2H ethanoic acid acetic acid CH3CHO ethanal acetaldehyde
CH3CH2CO2H propanoic acid propionic acid CH3CH2CHO propanal propionaldehyde
CH3(CH2)2CO2H butanoic acid butyric acid CH3(CH2)2CHO butanal butyraldehyde
CH3(CH2)3CO2H pentanoic acid valeric acid CH3(CH2)3CHO pentanal valeraldehyde
CH3(CH2)4CO2H hexanoic acid caproic acid CH3(CH2)4CHO hexanal caproaldehyde

 Substituents locations are given using Greek letters (, , , , , .)

beginning with the carbon next to the carbonyl carbon, the -carbon.
O OH O O
CH3CHBrCH2C H CH3CHCH2CH2C H CH2C H
       
-bromobutyraldehyde -hydroxyvaleraldehyde -phenylacetaldehyde
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 IUPAC Nomenclature of Ketones

Ketones: in both open chains and rings:

alkane+one  “alkanone”
 The parent chain must contain the C=O group , and this chain is
numbered to give the carbonyl group as low a number as possible. In
cyclic ketones, the carbonyl group is assigned the number ‘1’.
1 2
O4 5 O
O
CH3 CHCCHCH3 C CH2 CH2 CH3
CH3 CCH2 CH3
1 2 3 4 Cl CH3 1 2 3 4

2-butanone 2-chloro-4-methyl-3-pentanone 1-phenyl-1-butanone

 Ketones are just below aldehydes in nomenclature priority.

 A ketone group is named as an ‘oxo’ substituent in an aldehyde.
O 4 1
H3C O
CH3CH2CCH2CHO
5 4 3 2 1
An olefinic ketone is named 2
3
as an ‘enone’, literally: 4-methyl-2-cyclohexen-1-one
3-oxopentanal “#-alken-#-one”.
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 Common Names of Ketones

:O:  The two alkyl groups attached to the carbonyl are

R C R' named and the word ‘ketone’ is added as a
separate word. It is literally ‘alkyl alkyl ketone’.
 The alkyl groups are listed alphabetically or in
alkyl alkyl ketone order of increasing size.

 As with aldehydes, substituents locations are given in common names

using Greek letters (, , , , , .) beginning with the -carbon. OCH3
O CH3   O O
CH3CHCCHCH3 C CH2CH2CH2
CH3CCH2CHCH3
Cl CH3   
methyl isobutyl ketone
-chloroethyl isopropyl ketone -methoxypropyl phenyl ketone
(MIBK)
O O O
C CH3 C C H
Some historic
names persist: acetophenone benzophenone benzaldehyde
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 Nomenclature Practice

 Name these in IUPAC and, where possible, common nomenclature.

O O O
F
CH2 C CH3 C H C H

(I) 1-phenyl-2-propanone (I) 4-fluorocyclohexane-1-carbaldehyde

(c) methyl benzyl ketone (I) 3-cylcopentene-1-carbaldehyde

 Draw the structures of the following compounds.

butanedial bromomethyl -bromoethyl ketone 2,4-pentanedione
O
O O O O
BrCH2 C CH2CH2Br H3C C
HCCH2CH2CH CH2 C CH3
O O
 And these:
CH3CH CH C H CH2 CH C CH3
(I) 2-butenal (I) 3-buten-2-one
(c) methyl vinyl ketone
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 Preparation of Aldehydes (2 Methods)

1. Mild oxidation of 1° Alcohols: (with anhydrous oxidants, PCC in CHCl2

or Collins reagent (CrO3 in pyridine). 1,3-cyclobutanedicarbaldehyde
O O
PCC in CH2Cl2
HOCH2 CH2OH
HC CH

Dry ice
2. Reduction of acid chlorides,esters, and nitriles. (solid CO2)
sublimes at
: O: –78°C.
..
acid chloride R C
.. :
Cl -78°C : O:
1equiv. Only 1 equivalent
: O: R C H of very cold DIBAH
.. 1 DIBAH is used to avoid
ester R C OR
.. +
aldehyde
2 H3O further reduction of
the aldehyde to an
nitrile R C N: alcohol.

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 Preparation of Aldehydes (2 Methods)

 Recall that 1° alcohols are readily oxidized to carboxylic acids by most

oxidants in aqueous media.
moderate to (Cr+6, HNO3, KMnO4, etc.)
strong oxidation

: O: moderate to : O:
R OH mild oxidation
strong oxidation ..
R C R C OH
H ..
1° alcohol Jones reagent carboxylic acid
CrO3 in N aldehyde
CrO3 in H2SO4
or
PCC in CH2Cl2
1 LiAlH4
+
2 H3O

 In non aqueous media, moderate to strong oxidants become mild,

oxidizing 1° alcohols only as far as the aldehyde.
 Carboxylic acids can be reduced to 1° alcohols with LiAlH4, but no
reagent has been found that will stop the reduction at the aldehyde.

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 Preparation of Aldehydes (2 Methods)

 Carboxylic acids are difficult to reduce and any reducing agent strong
enough to reduce them, e.g., LiAlH4, will not stop at the aldehyde but
always produces the 1° alcohol.
 Several ‘derivatives’ of carboxylic acids can be reduced to aldehydes
under carefully controlled conditions.
 Acid chlorides, esters, and nitriles are reduced to aldehydes using
very cold conditions (-78°C) and only 1 equivalent of a mild reducing
agent, ‘diisobutylaluminum hydride’ = DIBAH (usually in toluene).

CH3 H CH3 CH3 CH3 _

+ + H:
CH3CHCH2 Al CH2CHCH3 CH3CHCH2 Al H
CH2CHCH3
diisobutyl aluminum hydride (DIBAH) Al
H H
aluminum
 DIBAH is weaker than LiAlH4. DIBAH is neutral; LiAlH4 is ionic. hydride

 DIBAH is similar to AlH3 but is hindered by its bulky isobutyl groups.

 Only one mole of H:- is released per mole of DIBAH.

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 Preparation of Aldehydes (2 Methods)
 Study the following examples and note which groups are displaced by
the hydride (H:-) from DIBAH.
toluene propanal
O O
1. DIBAH -78ºC
CH3CH2 C H + CH3OH
CH3CH2 C O CH3 +
2. H3O
methyl propanoate
_ CH3CH2C N
O _ NH3
HCl propanenitrile
CH3CH2 C Cl
propanoyl chloride

 Write equations showing the preparation of: PCC in CH2Cl2

O
a) pentanal from 1-pentanol or
CH3CH2CH2CH2CH
CH3CH2CH2CH2CH2OH CrO3 in N
b) butanal from an ester O -78°C
1equiv. O
CH3CH2CH2COCH3 CH3CH2CH2CH
c) benzaldehyde from a nitrile 1 DIBAH
-78°C O +
C N 2 H3O
1equiv.
C H
1 DIBAH
+ 17
2 H3O
 Preparation of Ketones (4 Methods)

1. Oxidation of 2° Alcohols: with mild (anhydrous) oxidants, moderate, or

strong oxidants, e.g., H2CrO4, HNO3, KMnO4, NaOCl, etc.

PCC (CH3 )3 C O
(CH3 )3 C OH
or Jones reagent
4-t-butylcyclohexanone

2. Friedel Crafts Acylation of Aromatics: yields ketones when an acid

chloride is used as the electrophile. O
O AlCl3
HO + CH3CH2 C Cl
HO C CH2CH3
EAS
propanoyl chloride 1-(4-hydroxyphenyl)propanone

3. Hydration of Alkynes: with Hg+2 and H3O+ yields an enol, that

‘tautomerizes’ to a ketone. O H
H
Hg(OAc)2 O
CH3 (CH2)3 C CH
CH3 (CH2)3 C CH CH3 (CH2)3 C CH
H3O+ H
1-hexyne 2-octanone
an enol H
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 Preparation of Ketones (4 Methods)

4. Acid Chlorides + Lithium Dialkyl Copper (Gilman Reagent):

produces ketones.
 The reaction is unique to these two reagents and the mechanism is
uncertain. As with DIBAH for aldehyde reductions, a low temperature (-
78 C) solvent (ether) is used to prevent further alkyl addition to the
ketone to form an alcohol. (Acid chlorides are very good electrophiles).
 Carboxylic acids, esters, anhydrides and amides are not reduced by
diorganocopper reagents. They are not as reactive as acid chlorides.
O - 78ºC O
CH3 (CH2)4 C
+ (CH3)2 Cu- Li+
Cl ether CH3 (CH2)4 C CH3
dimethyl copper lithium
hexanoyl chloride Gilman reagent 2-heptanone
 Recall that a stronger reducing reagent, such as a Grignard (RMgBr)
will also reduce an acid chloride to a ketone, but reduction cannot be
stopped here. The ketone is further reduced to an alcohol. ..
: O:
.. :O H
: O: :O:
.. CH3MgBr CH3MgBr +
2 H3O C
R C
.. :
Cl
R C CH3 R C CH3 R CH3
acid chloride ketone alkoxide CH3 3° alcohol CH3 19
 Preparation of Ketones Problems

 Write equations to show how the following transformations can be

carried out. Show all reagents and intermediate products.
a) 3-hexyne  3-hexanone OH O H
CH3CH2C CCH2CH3 CH3CH2C CCH2CH3 CH3CH2C CCH2CH3
+2 +
3-hexyne Hg , H3O H
3-hexanone H
b) benzene  m-bromoacetophenone O
: O: O Br
FeBr3 C
.. AlCl3 C CH3
CH3
+ H3C C
.. :
Cl
Br2 + HBr
acetyl chloride acetophenone m-bromoacetophenone
c) bromobenzene  acetophenone .. ..
: O: : OH
: O: O
Br MgBr H3O+ CH
Mg in ether CH CH3 Cr+6, H+ C
H C CH3 CH3 CH3

acetophenone
d) 1-methylcyclohexene  2-methylcyclohexanone
CH3 CH3 CH3
1 BH3, THF +6 +
Cr , H
2 NaOH, H2O2, pH8
OH O
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 Preparation of Ketones Problems

 Recall the effects of substituents on aromatic rings. They affect both

the reactivity of aromatics and the position at which Electrophilic
Aromatic Substitution (EAS) will occur.

o- and p- o- and p- m-directing

directing directing
O O
NH2 OCH3 CH3 F Br C OH SO3H NO2
CH

Reactivity Reactivity

H +
OH O Cl I O O C N N R3
NH C CH3 COCH3 C CH3
deactivators
activators deactivators

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