Bettelheim+12e Ch+16+PPT+2024-10-23+11 47 05

Introduction General
Organic, and
Biochemistry
Twelfth Edition
Bettelheim, Brown, Campbell, Farrell, Torres, Introduction General Organic, and Biochemistry, Twelfth Edition. © 2020
Cengage. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole
or in part.
Chapter 16
Aldehydes and Ketones
© 2020 Cengage. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly
accessible website, in whole or in part.
Isomers
The functional group of an aldehyde is a carbonyl group bonded to

a hydrogen atom.
• In methanal (formaldehyde), the simplest aldehyde, the carbonyl group is bonded
to two hydrogens.
• In other aldehydes, it is bonded to one hydrogen and one carbon group.
The functional group of a ketone is a carbonyl group bonded to two
carbon groups.
Nomenclature (1 of 5)
IUPAC names for aldehydes:

• To name an aldehyde, change the suffix -e of the parent alkane to -al.
• Because the carbonyl group of an aldehyde can only be at the end of a
parent chain and numbering must start with it as carbon-1, there is no
need to use a number to locate the aldehyde group.
• For unsaturated aldehydes, indicate the presence of a carbon–carbon
double bond by changing the ending of the parent alkane from -ane to -
enal. Numbering the carbon chain begins with the aldehyde carbonyl
carbon. Show the location of the carbon-carbon double bond by the
number of its first carbon.
• The IUPAC system retains common names for some

aldehydes, including these three.
IUPAC names for ketones.

• The parent alkane is the longest chain that contains the carbonyl group.
• Indicate the presence of the carbonyl group by changing the -ane of the
parent alkane -one.
• Number the parent chain from the direction that gives the carbonyl carbon
the smaller number.
• The IUPAC retains the common name acetone for 2-propanone.
To name an aldehyde or ketone that also contains an –OH (hydroxyl)

or –NH2 (amino) group:
• Number the parent chain to give the carbonyl carbon the lower number.
• Indicate an –OH substituent by hydroxy-, and an –NH2 substituent by amino-.
• Hydroxyl and amino substituents are numbered and alphabetized along with
other substituents.
Common names
The common name for an aldehyde is derived from the common
name of the corresponding carboxylic acid.
• Drop the word “acid” and change the suffix -ic or -oic to -aldehyde.
• Name each alkyl or aryl group bonded to the carbonyl carbon as a separate word,
followed by the word "ketone.” Alkyl or aryl groups are generally listed in order of
increasing molecular weight.
Physical Properties (1 of 3)
A C=O bond is polar, with oxygen bearing a partial negative

charge and carbon bearing a partial positive charge.
• Therefore, aldehydes and ketones are polar molecules.
• Figure 16.1 The polarity of a carbonyl group.
• In liquid aldehydes and ketones, there are weak intermolecular

attractions between the partial positive charge on the carbonyl
carbon of one molecule and the partial negative charge on the
carbonyl oxygen of another molecule.
• No hydrogen bonding is possible between aldehyde or ketone
molecules because they have no polar O–H or N–H bonds to
participate in hydrogen bonding.
• Aldehydes and ketones have lower boiling points than alcohols
and carboxylic acids, compounds in which there is hydrogen
bonding between molecules. See the table on the next screen.
accessible website, in whole or in part. 1
Table 16.1 Boiling Points for Six Compounds of Comparable Molecular Weight.
Name Structural Formula Molecular Weight (amu) Boiling Point (°C)
diethyl ether CH3CH2OCH2CH3 74 34
pentane CH3CH2CH2CH2CH3 72 36
butanal CH3CH2CH2CHO 72 76
2-butanone CH3CH2COCH3 72 80
1-butanol CH3CH2CH2CH2OH 74 117
propanoic acid CH3CH2COOH 74 141
• Formaldehyde, acetaldehyde, and acetone are infinitely soluble in water.
• Aldehydes and ketones become less soluble in water as the hydrocarbon portion of the
molecule increases in size.
Oxidation (1 of 2)
• Aldehydes are oxidized to carboxylic acids by a variety of oxidizing

agents, including potassium dichromate.
• Liquid aldehydes are so sensitive to oxidation by O2 in the air that they

must be protected from contact with air during storage.
Oxidation (2 of 2)
• Ketones resist oxidation by most oxidizing agents,

including potassium dichromate and molecular oxygen.
• Tollens’ reagent is specific for the oxidation of
aldehydes. If done properly, silver deposits on the walls
of the container as a silver mirror.
Reduction (1 of 4)
• The carbonyl group of an aldehyde or ketone is reduced to a –

C(H)OH group by hydrogen in the presence of a transition-
metal catalyst.
• Reduction of an aldehyde gives a primary alcohol.
• Reduction a ketone gives a secondary alcohol.
Reduction (2 of 4)
The most common laboratory reagent for the reduction of an

aldehyde or ketone is sodium borohydride, NaBH4.
• This reagent contains hydrogen in the form of hydride ion, H:–.
• In a hydride ion, hydrogen has two valence electrons and bears a
negative charge.
• In a reduction by sodium borohydride, hydride ion adds to the partially
positive carbonyl carbon which leaves a negative charge on the
carbonyl oxygen.
• Reaction of this intermediate with aqueous acid gives the alcohol.
Reduction (3 of 4)
• Reduction by NaBH4 does not affect a carbon-carbon double

bond or an aromatic ring.
Reduction (4 of 4)
• In biological systems, the agent for the reduction of aldehydes and

ketones is the reduced form of nicotinamide adenine dinucleotide,
abbreviated NADH (Section 26.3)
• This reducing agent, like NaBH4, delivers a hydride ion to the carbonyl carbon of the
aldehyde or ketone.
• Reduction of pyruvate, the end product of glycolysis, by NADH gives lactate.
Addition of Alcohols (1 of 4)
Addition of a molecule of alcohol to the carbonyl group of an aldehyde or

ketone forms a hemiacetal (a half-acetal).
• The functional group of a hemiacetal is a carbon bonded to one –OH group and
one -–OR group.
• In forming a hemiacetal, –H of the alcohol adds to the carbonyl oxygen and
–OR adds to the carbonyl carbon.
• Hemiacetals are generally unstable and are only minor

components of an equilibrium mixture except in one very
important type of molecule.
• When a hydroxyl group is part of the same molecule that contains
the carbonyl group and a five- or six-membered ring can form,
the compound exists almost entirely in a cyclic hemiacetal form.
A hemiacetal can react further with an alcohol to form an

acetal plus water.
• This reaction is acid-catalyzed.
• The functional group of an acetal is a carbon bonded to two –OR groups.
• All steps in hemiacetal and acetal formation are reversible.

• As with any other equilibrium, we can drive it in either direction by
using Le Chatelier's principle.
• To drive it to the right, we either use a large excess of alcohol or
remove water from the equilibrium mixture
• To drive it to the left, we use a large excess of water.
Mechanism of Acetal Formation (1 of 6)
Step 1: Add a proton.

Adding a proton to the carbonyl oxygen makes the carbonyl
carbon stronger electrophile and more susceptible to attack
by a nucleophile.
Step 2: Reaction of an electrophile and a nucleophile to

form a new covalent bond.
This step adds the first –OR group required for acetal
formation. The intermediate formed is an oxonium ion.
Step 3: Proton transfer to another oxygen.

The proton transferred is in red.
Step 4: Break a bond to form stable molecules or ions.

In this case the stable molecule is H2O and the stable ion is
a 3°carbocation.
Step 5: Reaction of an electrophile and a nucleophile to

form a new covalent bond.
This step adds the second –OR group of the acetal to what
was the original carbonyl carbon.
Step 6: Take a proton away.

Transfer of a proton to solvent gives the acetal and
regenerates the H+ catalyst.
Keto-Enol Tautomerism (1 of 4)
A carbon atom adjacent to a carbonyl group is called an a-

carbon, and a hydrogen atom bonded to it is called an a-
hydrogen.
An aldehyde or ketone that has a hydrogen on an a-carbon

is in equilibrium with a constitutional isomer called an enol.
• The name “enol” is derived from the IUPAC designation of it
as both an alkene (-en-) and an alcohol (-ol).
• In a keto-enol equilibrium, the keto form generally redominates.

Example 16.8: Draw structural formulas for the two enol

forms for each ketone.
Example 16.8: Draw structural formulas for the two enol

forms for each ketone.
Solution:
Problem 16.6
• Here are structural formulas

of two steroid hormones.
Name the functional groups
present in each.
Chapter 16 Aldehydes and Ketones
End
Chapter 16

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Introduction General

Aldehydes and Ketones

The functional group of an aldehyde is a carbonyl group bonded to

IUPAC names for aldehydes:

• The IUPAC system retains common names for some

IUPAC names for ketones.

To name an aldehyde or ketone that also contains an –OH (hydroxyl)

A C=O bond is polar, with oxygen bearing a partial negative

• In liquid aldehydes and ketones, there are weak intermolecular

• Aldehydes are oxidized to carboxylic acids by a variety of oxidizing

• Liquid aldehydes are so sensitive to oxidation by O2 in the air that they

• Ketones resist oxidation by most oxidizing agents,

• The carbonyl group of an aldehyde or ketone is reduced to a –

The most common laboratory reagent for the reduction of an

• Reduction by NaBH4 does not affect a carbon-carbon double

• In biological systems, the agent for the reduction of aldehydes and

Addition of a molecule of alcohol to the carbonyl group of an aldehyde or

• Hemiacetals are generally unstable and are only minor

A hemiacetal can react further with an alcohol to form an

• All steps in hemiacetal and acetal formation are reversible.

Step 1: Add a proton.

Step 2: Reaction of an electrophile and a nucleophile to

Step 3: Proton transfer to another oxygen.

Step 4: Break a bond to form stable molecules or ions.

Step 5: Reaction of an electrophile and a nucleophile to

Step 6: Take a proton away.

A carbon atom adjacent to a carbonyl group is called an a-

An aldehyde or ketone that has a hydrogen on an a-carbon

• In a keto-enol equilibrium, the keto form generally redominates.

Example 16.8: Draw structural formulas for the two enol

Example 16.8: Draw structural formulas for the two enol

• Here are structural formulas

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