Aldehydes & Ketones

Aldehydes and Ketones
1
Carbonyl Compounds
2
Carbonyl Structure
 Carbon is sp2 hybridized.

 C═O bond is shorter, stronger, and more polar
than C═C bond in alkenes.
3
Carbonyl Structure
 The functional group of an aldehyde is a carbonyl
group bonded to a H atom and a carbon 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)
Ketone Nomenclature
O O
1 3 4 1 3 4
CH3 C CH CH3 CH3 C CH CH2OH
2 2 CH
CH3 3
3-methyl-2-butanone 4-hydroxy-3-methyl-2-butanone
 Number the chain so that carbonyl carbon

has the lowest number.
 Replace the alkane -e with -one.
5
Ketone Nomenclature (Continued)
1 O
3
Br
3-bromocyclohexanone
 For cyclic ketones, the carbonyl carbon is

assigned the number 1.
6
Aldehydes Nomenclature
CH3 O
CH3 CH2 CH CH2 C H
5 3 2 1
3-methylpentanal
 The aldehyde carbon is number 1.

 IUPAC: Replace -e with -al.
7
Nomenclature
Carbonyl as Substituent
 On a molecule with a higher priority
functional group, a ketone is an oxo and an
aldehyde is a formyl group.
 Aldehydes have a higher priority than ketones.
1 COOH
O CH3 O
CH3 C CH CH2 C H 3
4 3 1
CHO
3-methyl-4-oxopentanal 3-formylbenzoic acid

8
Nomenclature
Common Names for Ketones
 Named as alkyl attachments to —C═O.
 Use Greek letters instead of numbers.
O O
CH3 C CH CH3 CH3CH C CH CH3
CH3 Br CH3
methyl isopropyl ketone bromoethyl isopropyl ketone
9
Nomenclature
Historical Common Names
O
C
O CH3
CH3 C CH3
acetone acetophenone
O
C
benzophenone
10
Order of Precedence
 For compounds that contain more than one
functional group indicated by a suffix
Functional Suffix If Higher Prefix If Lower
Group in Precedence in Precedence
Increasing precedence
- COOH -oic acid

- CHO -al oxo-
C= O -one oxo-
- OH -ol hydroxy-
- SH -thiol -sulfanyl
- NH2 -amine -amino
Boiling Points
 Ketones and aldehydes are more polar, so they

have a higher boiling point than comparable
alkanes or ethers.
 They cannot hydrogen-bond to each other, so
their boiling point is lower than comparable
alcohol.
12
Solubility of Ketones and Aldehydes
 Good solvent for
alcohols.
 Lone pair of electrons on
oxygen of carbonyl can
accept a hydrogen bond
from O—H or N—H.
 Acetone and
acetaldehyde are
miscible in water.
13
Formaldehyde
H H
C O HO
O O heat H 2O OH
H H C H H C
C C H H
O formaldehyde,
H H formalin
b.p. -21C
trioxane, m.p. 62C
 Gas at room temperature.

 Formalin is a 40% aqueous solution.
14
Industrial Importance
 Acetone and methyl ethyl ketone are important solvents.

 Formaldehyde is used in polymers
like Bakelite (trademark of phenol-
formaldehyde resin).
 Flavorings and additives like vanilla, cinnamon, and
artificial butter.
15
16
Preparation of Aldehydes and Ketones
Oxidation of Secondary Alcohols to Ketones
 Secondary alcohols are readily oxidized to ketones

with sodium dichromate (Na2Cr2O7) in sulfuric acid
or by potassium permanganate (KMnO4).
17
Mechanism of Oxidation by Chromium(VI)
18
Oxidation of Primary Alcohols to Aldehydes
 Pyridinium chlorochromate (PCC) is

selectively used to oxidize primary
alcohols to aldehydes.
19
20
Ozonolysis of Alkenes
 The double bond is oxidatively

cleaved by ozone followed by
reduction.
21
Mechanism for Oxidation by Ozonolysis
22
Friedel–Crafts Reaction
 Reaction between an acyl halide and an aromatic

ring will produce a ketone.
23
Hydration of Alkynes
 The initial product of Markovnikov hydration is an enol,

which quickly tautomerizes to its keto form.
 Internal alkynes can be hydrated, but mixtures of ketones
often result.
24
Mechanism for Hydration of Alkynes
25
Hydroboration–Oxidation of Alkynes
 Hydroboration–oxidation of an alkyne gives anti-

Markovnikov addition of water across the triple bond.
26
Hydroboration–Oxidation of Alkynes
Chapter 18 27
Solved Problem 1
Show how you would synthesize each compound from starting materials
containing no more than six carbon atoms.
(a (b
) )
Solution
(a) This compound is a ketone with 12 carbon atoms. The carbon skeleton
might be assembled from two six-carbon fragments using a Grignard
reaction, which gives an alcohol that is easily oxidized to the target
compound.
28
Solved Problem 1 (Continued)
Solution (Continued)
An alternative route to the target compound involves Friedel–
Crafts acylation.
(b) Thiscompound is an aldehyde with eight carbon atoms. An aldehyde

might come from oxidation of an alcohol (possibly a Grignard product)
or hydroboration of an alkyne. If we use a Grignard, the restriction to
six-carbon starting materials means we need to add two carbons to a
methylcyclopentyl fragment, ending in a primary alcohol. Grignard
addition to an epoxide does this.
29
Solution (Continued)
Alternatively, we could construct the carbon skeleton
using acetylene as the two-carbon fragment. The
resulting terminal alkyne undergoes hydroboration to
the correct aldehyde.
(b)
30
Synthesis of Ketones and Aldehydes Synthesis
of Ketones from Carboxylic Acids
 Organolithiums will attack the lithium salts of

carboxylate anions to give dianions.
 Protonation of the dianion forms the hydrate of
a ketone, which quickly loses water to give the
ketone.
31
Synthesis of Ketones and Aldehydes Ketones
from Nitriles
 A Grignard or organolithium reagent can

attack the carbon of the nitrile.
 The imine is then hydrolyzed to form a ketone.
32
Synthesis of Ketones and Aldehydes
Aldehydes from Acid Chlorides
 Lithium aluminum tri(t-butoxy)hydride is a

milder reducing agent that reacts faster with
acid chlorides than with aldehydes.
33
Synthesis of Ketones and Aldehydes
Lithium Dialkyl Cuprate Reagents
 A lithium dialkylcuprate (Gilman reagent)

will transfer one of its alkyl groups to the
acid chloride.
34
Reactions of Aldehydes and Ketones
Nucleophilic Addition
 A strong nucleophile attacks the carbonyl carbon,

forming an alkoxide ion that is then protonated.
 Aldehydes are more reactive than ketones.
35
The Wittig Reaction
 The Wittig reaction converts the carbonyl

group into a new C═C double bond where
no bond existed before.
 A phosphorus ylide is used as the
nucleophile in the reaction.
36
Preparation of Phosphorus Ylides
 Prepared from triphenylphosphine and an

unhindered alkyl halide.
 Butyllithium then abstracts a hydrogen from
the carbon attached to phosphorus.
37
Mechanism of the Wittig Reaction
Betaine formation
Oxaphosphetane formation
38
Mechanism of the WittigReaction (continued)
 The oxaphosphetane will collapse, forming the

alkene and a molecule of triphenyl phosphine
oxide.
39
Solved Problem 2
Show how you would use a Wittig reaction to
synthesize 1-phenyl-1,3-butadiene.
40
Solution
This molecule has two double bonds that might be formed by Wittig
reactions. The central double bond could be formed in either of two ways.
Both of these syntheses will probably work, and both will produce a
mixture of cis and trans isomers.
You should complete this solution by drawing out the

syntheses indicated by this analysis 41
Hydration of Ketones and Aldehydes
 In an aqueous solution, a ketone or an

aldehyde is in equilibrium with its hydrate, a
geminal diol.
 With ketones, the equilibrium favors the
unhydrated keto form (carbonyl).
42
Mechanism of Hydration of Ketones and Aldehydes
 Hydration occurs through the nucleophilic

addition mechanism, with water (in acid) or
hydroxide (in base) serving as the
nucleophile.
43
Cyanohydrin Formation
 The mechanism is a base-catalyzed

nucleophilic addition: Attack by cyanide ion
on the carbonyl group, followed by
protonation of the intermediate.
 HCN is highly toxic.
44
Formation of Imines
 Ammonia or a primary amine reacts with a ketone or

an aldehyde to form an imine (Schiff base)
 Imines are nitrogen analogues of ketones and
aldehydes with a C═N bond in place of the carbonyl
group.
 Optimum pH is around 4.5
45
Mechanism of Imine Formation
Acid-catalyzed addition of the amine to the carbonyl
group leads to a carbinolamine
Acid-catalyzed dehydration of the carbinolamine gives the imine
46
Other Condensations with Amines
47
Formation of Acetals
48
Mechanism for Hemiacetal Formation
 Must be acid-catalyzed.
 Adding H+ to carbonyl makes it more
reactive with weak nucleophile, ROH.
49
Acetal Formation
50
Cyclic Acetals
 Addition of a diol produces a cyclic acetal.

 The reaction is reversible.
 This reaction is used in synthesis to protect
carbonyls from reaction
51
Acetals as Protecting Groups
O O
HO O
OH
H +
H
H
O O
 Hydrolyze easily in acid; stable in base.

 Aldehydes are more reactive than ketones.
52
Reaction and Deprotection
O
O O
1) NaBH4
H 2) H3O+ H
O OH
 The acetal will not react with NaBH4, so only the

ketone will get reduced.
 Hydrolysis conditions will protonate the alcohol
and remove the acetal to restore the aldehyde.
53
Oxidation of Aldehydes
Aldehydes are easily oxidized to carboxylic acids.

54
Reducing Reagents
 Sodium borohydride, NaBH4, can reduce ketones
to secondary alcohols and aldehydes to primary
alcohols.
 Lithium aluminum hydride, LiAlH4, is a powerful
reducing agent, so it can also reduce carboxylic
acids and their derivatives.
 Hydrogenation with a catalyst can reduce the
carbonyl, but it will also reduce any double or
triple bonds present in the molecule.
55
Sodium Borohydride
O OH
NaBH4
R R(H) CH3OH R R(H)
H
aldehyde or ketone
• NaBH4 can reduce ketones and

aldehydes, but not esters, carboxylic
acids, acyl chlorides, or amides.
56
Lithium Aluminum Hydride
O OH
LiAlH4
R R(H) ether R R(H)
H
aldehyde or ketone
 LiAlH4 can reduce any carbonyl because it is

a very strong reducing agent.
 Difficult to handle.
57
Catalytic Hydrogenation
O OH
H2
Raney Ni
 Widely used in industry.

 Raney nickel is finely divided Ni powder saturated
with hydrogen gas.
 It will attack the alkene first, then the carbonyl.
58
Deoxygenation of Ketones and Aldehydes
 The Clemmensen reduction or the Wolff–

Kishner reduction can be used to
deoxygenate ketones and aldehydes.
59
Clemmensen Reduction
O
C CH2CH2CH3
CH2CH3 Zn(Hg)
HCl, H2O
O
Zn(Hg)
CH2 C CH2 CH3
H HCl, H2O
60
Wolff–Kishner Reduction
 Forms hydrazone, then heat with strong base like

KOH or potassium tert-butoxide.
 Use a high-boiling solvent: ethylene glycol,
diethylene glycol, or DMSO.
 A molecule of nitrogen is lost in the last steps of
the reaction.
61

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Aldehydes and Ketones

 Carbon is sp2 hybridized.

 Number the chain so that carbonyl carbon

 For cyclic ketones, the carbonyl carbon is

 The aldehyde carbon is number 1.

3-methyl-4-oxopentanal 3-formylbenzoic acid

methyl isopropyl ketone bromoethyl isopropyl ketone

- COOH -oic acid

 Ketones and aldehydes are more polar, so they

 Gas at room temperature.

 Acetone and methyl ethyl ketone are important solvents.

 Secondary alcohols are readily oxidized to ketones

 Pyridinium chlorochromate (PCC) is

 The double bond is oxidatively

 Reaction between an acyl halide and an aromatic

 The initial product of Markovnikov hydration is an enol,

 Hydroboration–oxidation of an alkyne gives anti-

(b) Thiscompound is an aldehyde with eight carbon atoms. An aldehyde

 Organolithiums will attack the lithium salts of

 A Grignard or organolithium reagent can

 Lithium aluminum tri(t-butoxy)hydride is a

 A lithium dialkylcuprate (Gilman reagent)

 A strong nucleophile attacks the carbonyl carbon,

 The Wittig reaction converts the carbonyl

 Prepared from triphenylphosphine and an

 The oxaphosphetane will collapse, forming the

You should complete this solution by drawing out the

 In an aqueous solution, a ketone or an

 Hydration occurs through the nucleophilic

 The mechanism is a base-catalyzed

 Ammonia or a primary amine reacts with a ketone or

Acid-catalyzed dehydration of the carbinolamine gives the imine

 Addition of a diol produces a cyclic acetal.

 Hydrolyze easily in acid; stable in base.

 The acetal will not react with NaBH4, so only the

Aldehydes are easily oxidized to carboxylic acids.

• NaBH4 can reduce ketones and

 LiAlH4 can reduce any carbonyl because it is

 Widely used in industry.

 The Clemmensen reduction or the Wolff–

 Forms hydrazone, then heat with strong base like

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