Unit 3: Aldehydes and Ketones

UNIT LEARNING OUTCOMES

 Distinguish and differentiate aldehydes from ketones
 Demonstrate proficiency in naming and structure writing of hydrocarbon
containing carbonyl group
 Analyze and understand physical and chemical properties of aldehydes
and ketones including their preparations addition reactions, isomerism
 Identify common and important sources, practical uses and their
applications in industrial setting

ENGAGE

Source: https://www.health.com/food/health-benefits-almonds
Benzaldehyde is the main flavor component in almonds. Aldehydes and ketones are
responsible for the odor and taste of numerous nuts and spices.

Reflection 2.3: Identify one aldehyde/ketone found at home and take a selfie.
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 EXPLORE AND EXPLAIN

The Carbonyl Group

Both aldehydes and ketones contain a carbonyl functional group. A carbonyl
group is a carbon atom double-bonded to an oxygen atom. The structural
representation for a carbonyl group

The carbon–oxygen double bond is polarized, the oxygen atom acquiring a

fractional negative charge and the carbon atom acquiring a fractional positive
charge.

Aldehydes and Ketones

Aldehydes Ketones
 One alkyl or aromatic group and  Two alkyl (or aromatic) groups
one hydrogen bonded to a bonded to a carbonyl group
carbonyl

 General Formula: RCHO  General Formula: RCOR

 Alkanal Group  Alkanone Group
Cyclic ketones are not heterocyclic ring systems as were cyclic ethers.

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 Nomenclature of Phenol of Aldehydes and Ketones
A. IUPAC naming
Aldehydes are named by replacing the terminal -e of the corresponding
alkane name with -al. The parent chain must contain the -CHO group, and the -CHO
carbon is numbered as carbon 1. For cyclic aldehydes in which the -CHO group is
directly attached to a ring, the suffix -carbaldehyde is used.

Ketones are named by replacing the terminal -e of the corresponding alkane

name with -one. The parent chain is the longest one that includes the ketone group,
and the numbering begins at the end nearer the carbonyl carbon. As with alkenes
and alcohols, the locant is placed before the parent name using older rules but
before the suffix with the newer IUPAC guidelines.

Note the old IUPAC name was given first followed by the new IUPAC naming.

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 When it’s necessary to refer to the R-C=O as a substituent, the name acyl
(a-sil) group is used and the name ending -yl is attached.

If other functional groups are present and the double-bonded oxygen is

considered a substituent on a parent chain, the prefix oxo- is used. (Refer to
Functional Group Seniority Table)

B. Common Naming
In common names of aldehydes, the parent name is aldehyde and the stems
used are based from which it is first isolated (carboxylic acids) The stems for the first
10 aldehydes are as follows:
1 carbon atom: form- 6 carbon atom: capro-
2 carbon atoms: acet- 7 carbon atoms: enanth-
3 carbon atoms: propion- 8 carbon atoms: capryl-
4 carbon atoms: butyr- 9 carbon atoms: pelargon-
5 carbon atoms: valer 10 carbon atoms: capr-
Also the carbon atoms near the carbonyl group are often designated by
Greek letters.

For example:

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 In common naming of ketones, it consists of the names of the groups attached
to the carbonyl group, followed by the word ketone. (Note the similarity to the
naming of ethers.)

Below are a few aldehydes and ketones that are recognized by IUPAC.
Common Name of Some
Ketones

Physical Properties of Aldehydes and Ketones

 Higher boiling points than alkanes with same molar mass but lower than that
of alcohols and carboxylic acids due to stronger hydrogen bonding
 Lower molecular weight aldehydes & ketones are soluble in water; borderline
solubility is 5 carbon atoms
 Low molecular weight aldehydes have disagreeable penetrating odors; but
as molecular weight increases, becomes more fragrant
 More polar than ether and alkanes
 These solubility properties are similar to those of ethers and alcohols which also
engage in hydrogen bonding with water.
 Due to hydrogen bonding, ketones and aldehydes are good solvents for polar
hydroxylic substances such as alcohols.

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 Reactions of Aldehydes and Ketones
1. Preparation of Aldehydes and Ketones
a. Oxidation of Primary Alcohol to
Aldehydes. Pyridinium dichromate
(PDC) or pyridinium chlorochromate
(PDC) in anhydrous media such as
dichloromethane oxidizes primary
alcohols to aldehydes while
avoiding overoxidation to
carboxylic acids.

b. Oxidation of Secondary Alcohol

to Ketones. Some oxidizing agents
available for converting secondary
alcohols to ketones are PDC or PCC
may be used as well as other Cr(IV)-
based agents such as chromic acid
or potassium dichromate and
sulfuric acid.

c. Oxidation of methylbenzene Ar-CH3  Ar-CHCl 2  Ar-CHO

d. Reduction of acid chlorides
(Friedel-Crafts). Reaction in the R-COCl / Ar-COCl  RCHO / Ar-CHO
presence of LiAlH4 (Lithium
Aluminum Hydride)

e. Ozonolysis of Alkene. The

substitution pattern around a
double bond is revealed by
identifying the carbonyl-containing
compounds that make up the
product.

2. Oxidation of Aldehydes and Ketones. Aldehydes readily undergo oxidation to

carboxylic acids and ketones are resistant to oxidation.

Common test based on the ease with which aldehydes are oxidized
Tollen’s Test. General Test for Aldehydes Benedict’s Test: for Aliphatic Aldehydes

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 3. Reduction of Aldehydes and Ketones. Aldehydes and ketones are easily reduced
by hydrogen gas (H2), in the presence of a catalyst (Ni, Pt, or Cu), to form alcohols.
Also, reduction with sodium borohydride or lithium aluminum hydride are general
methods.
Aldehydes Ketones

4. Addition of Grignard reagents and organolithium compounds. Aldehydes are

converted to alcohols and ketones to tertiary alcohol.

5. Nucleophilic addition. The most important chemical property of the carbonyl

group it its tendency to undergo nucleophilic addition reactions as shown.

a. Hydration of Aldehydes and Ketones. Aldehydes and Ketones react with water in
a rapid equilibrium.

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 b. Cyanohydrin Formation. The product addition to hydrogen cyanide to an
aldehyde or ketone contains both a hydroxyl group and a cyano group bonded on
the same carbon. Compounds of this type are called cyanohydrins.

c. Hemiacetal formation. Hemiacetal formation is an addition reaction in which a

molecule of alcohol adds to the carbonyl group of an aldehyde or ketone. The H
portion of the alcohol adds to the carbonyl oxygen atom, and the R—O portion of
the alcohol adds to the carbonyl carbon atom.

A hemiacetal is an organic compound in which a carbon atom is

bonded to both a hydroxyl group (-OH) and an alkoxy group (-OR).
The functional group for a hemiacetal is shown to your right.
For example:

\
d. Wittig Reaction. It uses phosphorus ylides (called Wittig reagents) to convert
aldehydes and ketones to alkenes. Wittig reaction ay be carried out in a number of
different solvents; normally tetrahydrofuran (THF) or dimethyl sulfoxide (DMSO) is
used.

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 Common Aldehydes and Ketones and its Uses
a. Formaldehyde
 simplest aldehyde
 Its major use is in the manufacture of polymers
 formalin, an aqueous solution containing 37% formaldehyde by mass or 40%
by volume.
 Formalin is used for preserving biological specimens
b. Acetone
 a colorless, volatile liquid with a pleasant, mildly “sweet” odor
 the simplest ketone
 excellent solvent because
 main ingredient in gasoline treatments
 used to remove water from glassware in the laboratory
 major component of some nail polish removers.
c. Acetaldehyde - has a general narcotic action; used as an intermediate in the
manufacture of acetic acid and 1-butanol.
d. Paraldehyde – used as a sedative
e. Metaldehyde – an ingredient in some pesticides; attractive and highly poisonous
to slugs and snails. Also used as a solid fuel.
f. Some aldehydes and ketones are used as flavorings and oil extracts

g. Many important steroid hormones are ketones, including testosterone,the

hormone that controls the development of male sex characteristics; progesterone,
the hormone secreted at the time of ovulation in females; and cortisone, a hormone
from the adrenal glands that is used medicinally to relieve infl ammation.

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 ELABORATE
Graded Assignment 2.3: Concept Application: Show all necessary computations
and or illustrations.
(1) Complete the table
Give the IUPAC Name Identify if Draw the condensed
aldehyde or structure
ketone
1. 6.

2. 7.

3. 8.

4. 9.

5. 10.

o-bromobenzaldehyde 11. 16.

acetone 12. 17.
2-methylcyclobutanone 13. 18.
3-ethylcyclopentanecarbaldehyde 14. 19.
8-bromo-2-methyloctanal 15. 20.
B. Give all possible and complete reaction for the following. Properly name the
organic compound.
1. Nucleophilic addition for of p-methylbenzaldehyde with oxygen.
2. Reduction of 4-ethylheptanal
3. Oxidation of 2,4-pentanedione
4. Addition of Grignard reagents
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EVALUATE

Graded Test 6: Concept Analysis/Application

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