ALDEHÍDOS Y CETONAS

Presentado por:
Profa. Berenice Tierrablanca
Gudiño
Carbonyl Compounds

Chapter 18 2
Carbonyl Structure

• Carbon is sp2 hybridized.

• C═O bond is shorter, stronger, and more polar
than C═C bond in alkenes.

Chapter 18 3
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.

Chapter 18 4
Ketone Nomenclature (Continued)
1 O

3-bromocyclohexanone
3
Br

• For cyclic ketones, the carbonyl carbon is assigned the number 1.

Chapter 18 5
Aldehydes Nomenclature
CH3 O
5 2
CH3 CH2 CH CH2 C H
3 1
3-methylpentanal

• The aldehyde carbon is number 1.

• IUPAC: Replace -e with -al.

Chapter 18 6
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

Chapter 18 7
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 a-bromoethyl isopropyl ketone

Chapter 18 8
Historical Common Names
O
C
O CH3
CH3 C CH3
acetone acetophenone
O
C

benzophenone

Chapter 18 9
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.

Chapter 18 10
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.

Chapter 18 11
Chapter 18 12
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).

Chapter 18 13
Oxidation of Primary Alcohols to Aldehydes

• Pyridinium chlorochromate (PCC) is selectively

used to oxidize primary alcohols to aldehydes.

Chapter 18 14
Ozonolysis of Alkenes

• Se pueden separar los aldehídos y cetonas

Chapter 18 15
Ozonolysis
Mechanism for Ozonide Formation
The Ozonide is Converted to
Ketones and/or Aldehydes
Ozonolysis
Ozonolysis
What Alkene Gave the Ozonolysis Products?
Friedel–Crafts Reaction

• Reaction between an acyl halide and an aromatic

ring will produce a ketone.

Chapter 18 22
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.
Chapter 18 23
Synthesis of Ketones and Aldehydes Using 1,3-
Dithianes

• 1,3-Dithiane can be deprotonated by strong bases

such as n-butyllithium.
• The resulting carbanion is stabilized by the
electron-withdrawing effects of two polarizable
sulfur atoms.
Chapter 18 24
Alkylation of 1,3-Dithiane

• Alkylation of the dithiane anion by a primary alkyl

halide or a tosylate gives a thioacetal that can be
hydrolyzed into the aldehyde by using an acidic
solution of mercuric chloride.

Chapter 18 25
Ketones from 1,3-Dithiane

• The thioacetal can be isolated and deprotonated.

• Alkylation and hydrolysis will produce a ketone.

Chapter 18 26
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.
Chapter 18 27
Ketones from Nitriles

• A Grignard or organolithium reagent can attack the carbon of the

nitrile.
• The imine is then hydrolyzed to form a ketone.

Chapter 18 28
Lithium Dialkyl Cuprate Reagents

• A lithium dialkylcuprate (Gilman reagent) will

transfer one of its alkyl groups to the acid chloride.

Chapter 18 29
Nucleophilic Addition

• A strong nucleophile attacks the carbonyl carbon,

forming an alkoxide ion that is then protonated.
• Aldehydes are more reactive than ketones.

Chapter 18 30
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).

Chapter 18 31
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.

Chapter 18 32
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.

Chapter 18 33
Formation of Imines

• Ammonia or a primary amine reacts with a ketone or an

aldehyde to form an imine.
• 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

Chapter 18 34
 Mechanism of Imine Formation
Acid-catalyzed addition of the amine to the carbonyl
compound group.

Acid-catalyzed dehydration.

Chapter 18 35
Other Condensations with Amines

Chapter 18 36
Formation of Acetals

Chapter 18 37
Mechanism for Hemiacetal Formation

• Must be acid-catalyzed.
• Adding H+ to carbonyl makes it more reactive with
weak nucleophile, ROH.

Chapter 18 38
Acetal Formation

Chapter 18 39
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

Chapter 18 40
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.

Chapter 18 41
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.

Chapter 18 42
Oxidation of Aldehydes

Aldehydes are easily oxidized to carboxylic acids.

Chapter 18 43
Reduction 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.

Chapter 18 44
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.

Chapter 18 45
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.

Chapter 18 46
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.

Chapter 18 47
Deoxygenation of Ketones and Aldehydes

• The Clemmensen reduction or the Wolff–Kishner

reduction can be used to deoxygenate ketones and
aldehydes.

Chapter 18 48
Clemmensen Reduction
O
C CH2CH2CH3
CH2CH3 Zn(Hg)
HCl, H2O

O
Zn(Hg)
CH2 C CH2 CH3
H HCl, H2O

Chapter 18 49
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.
Chapter 18 50