Lecture Notes 7

General Chemistry
(CHM111)
First Semester 2021/2022
 General Chemistry
Fourth Edition

Julia Burdge

Lecture PowerPoints

Carbonyl Compounds,
Carboxylic Acids and
Amines

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Aldehydes and Ketones

3
 Aldehydes and Ketones

carbonyl compounds with hydrogen and alkyl groups

• Formaldehyde: two hydrogen
• Aldehyde: a hydrogen and an alkyl group
• Ketone: two alkyl groups

© 2014 Pearson Education, Inc.

 Nomenclature of Aldehydes
• Aldehydes contain the formyl group (–CHO). They are named
by replacing –e in the name of the parent alkane with –al

• Aldehydes take precedence over alcohols (ranking is done

by oxidation state)

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5
 Nomenclature of Aldehydes

© 2014 Pearson Education, Inc.

 Nomenclature of Ketones
• To name ketones, –e in the name of the parent alkane is
replaced with –one
• The carbonyl carbon is given a locant (smallest possible); C–
1 in cyclic ketones

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7
 Common Ketones
• A few ketones have acceptable common names (all of which end in –one)

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8
 Ketone Nomenclature
• Number the chain so that the carbonyl carbon has the lowest number.
• Replace the alkane -e with -one.

© 2013 Pearson Education, Inc. Chapter 18

9 9
 Nomenclature of Ketones

© 2014 Pearson Education, Inc.

Ketones and Naming

11
Physical Properties
• Aldehydes and ketones experience strong dipole-
dipole forces
• Boiling
and melting points are generally higher than
alkenes of comparable molecular weight
• Boiling
and melting points are lower than related
alcohols, however

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12
 Aldehydes and Ketones
Found in Nature

© 2014 Pearson Education, Inc.

 Reactions of Aldehydes and Ketones
A.Nucleophilic Addition of the nucleophile to the partial
positively charged C-atom in the carbonyl group

1. Water (nucleophil is Od-) leads to Diols (also called hydrates)

2. Alcohol (acid-catalyzed, nucleophile is Od-)

Aldehyde changes to hemiacetal, then to acetal
Ketone changes to hemiketal, then to ketal

B. Oxidation

C. Reduction

14
 Addition Reactions
of Aldehydes and Ketones
• A. Nucleophilic Addition of the nucleophile to the partial
positively charged C-atom in the carbonyl group

15
Nucleophilic Addition Reactions
of Aldehydes and Ketones
• Nucleophiles can be negatively charged (:Nu -) or
• neutral (:Nu) at the reaction site

16
 1. Addition of H2O (Hydration)
• Addition of water to the carbonyl group of an aldehyde or
ketone gives
• a hydrate, also called geminal diol (gem-diol)

17
 2. Addition of Alcohols
▪ Addition
of one molecule of alcohol to the C=O group of
an aldehyde or ketone gives a hemiacetal.
▪ Hemiacetal:
A molecule containing an -OH and an -OR or -
OAr bonded to the same carbon.

18
 2. Addition of Alcohols
▪ Hemiacetalsreact with alcohols to form acetals.
Acetal: A molecule containing two -OR or -OAr
groups bonded to the same carbon.

19
 2. Addition of Alcohols
• acid-catalyzed, nucleophile is Od-
Aldehyde changes to hemiacetal, then to acetal
Ketone changes to hemiketal, then to ketal

20
 (B) Oxidation

Oxidation means
• Loss of electron or
• Loss of hydrogen or
• Gain of Oxygen

21
 (B) Oxidation of Aldehydes
• Aldehydes oxidize readily to form carboxylic
acids.
• Ketones do not undergo oxidation.

Oxidation
• Loss of electron or
• Loss of hydrogen or
• Gain of Oxygen

Chapter 23/22
 Oxidation of Aldehydes
Aldehydes are easily oxidized to carboxylic acids.

Chapter 23/23
 Oxidation of Aldehydes and Ketones
Aldehydes are turned to carboxylic acids
The oxidation happens with following tests :
• Benedict’s reagent (Cu2+)citrate complex
• Fehlings Test (Cu2+) tartrate complex
• Tollens Test (Ag+)

Ketones need strong oxidation agents because C-C bonds

need to be broken by
• Vigorous oxidation with KMnO4 or conc. HNO3
24
 (C) Reduction of Aldehydes and
Ketones
Reduction
Aldehydes change to prim. Alcohols
• Gain of electron or
Ketons change to sec. Alcohols
• Gain of hydrogen or
or change to alkanes • Loss of Oxygen
by
1. Metal Hydride Reduction (laboratory reagents NaBH4 and LiAlH4)
2. Catalytic Hydrogenation (H2, Pt, Heat, Pressure)

O OH
Pt
+ H2
25 o C, 2 atm
Cyclohexanone Cyclohexanol 25
 Reduction of Aldehydes and
Ketones
 Aldehydes can be reduced to 1° alcohols.
 Ketones can be reduced to 2° alcohols.
 The C=O group of an aldehyde or ketone can be reduced
to a -CH2- group.

26
 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.

27
Carboxylic Acids

28
 Naming Carboxylic Acids

In naming a carboxylic acid,

• the IUPAC name replaces the e in the alkane
name with oic acid.

• substituents are numbered by counting the

carbonyl carbon as carbon 1.

• common names are used for carboxylic acids

with four or less carbon atoms.

29
Names of Carboxylic Acids

The sour taste of vinegar is due to ethanoic acid (acetic acid).

30
IUPAC and Common Names:
Carboxylic Acids

31
IUPAC and Common Names:
Carboxylic Acids
• The carboxylic acid of benzene is named
benzoic acid.
• The carbon of the carboxyl group is bonded to
carbon 1 in the ring, and the ring is numbered to
give the lowest numbers for any substituents.

32
 Naming Carboxylic Acids
Write the IUPAC name for the following:

STEP 1 Identify the longest carbon chain and

replace the e in the alkane name with oic
acid.

STEP 2 Name and number any substituents by

counting the carboxyl carbon as 1.

33
 Naming Carboxylic Acids
• Many carboxylic acids are known by their common names
 Formic acid
 Acetic acid
 Benzoic acid
 Butyric acid
 Valeric acid
• In systematic names, –e in the parent alkane name is replaced with –oic
acid
 Propanoic acid

• To name diacids, replace –e in the parent alkane name with

–edioic acid
 Propanedioic acid (malonic acid) 34
Nomenclature of Carboxylic Acids

35
 Nomenclature of Carboxylic Acids

In systematic nomenclature, the carbonyl carbon is C-1.

In common nomenclature, the carbon next to the carbonyl is the alpha-carbon.

36
Nomenclature of Carboxylic Acids

37
 Synthesis of Carboxylic acids
•Oxidation

38
Synthesis of Carboxylic acids
•Oxidation

39
Reactions of RCO2H
Substitution of OH-Group (Addition of Nucleophile is followed by removing OH-Group)

40
Reactions of RCO2H
Reduction to 10 Alcohol (with LiAlH4)

41
Amines

42
 Amines
• Amines are organic derivatives of ammonia

• They have alkyl or

aryl groups (or H)
bound to nitrogen

• The basic lone pair on nitrogen dictates much of the reactivity

of amines

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Classification of Amines
Amines are classified as primary, secondary, or tertiary.
• A primary (1°) amine has one carbon group bonded to the
nitrogen atom.
• A secondary (2°) amine has two carbon groups bonded to the
nitrogen atom.
• A tertiary (3°) amine has three carbon groups bonded to the
nitrogen atom.
H N H H—N—CH3 CH3 —N—CH3

Chapter 23/44
CH3 CH3 CH3
1° 2° 3°
 Amines

Amines have one or more carbon

atoms bonded to the N atom.
45
 Classifying Amines

• Amines are classified according to their degree of

substitution at nitrogen
• Primary amines have one alkyl group, secondary
amines have two, and tertiary amines have three

46
 Aromatic Amines

Aromatic amines use

the name aniline, which
is approved by IUPAC.

Aniline is used to make

fabric dyes, including
indigo.

47
Naming Amines

48
 Low Priority of −𝐍𝐇𝟐
• The −NH2 group has low priority because the atomic
number of N is less than O
 Lower priority than alcohols
 Lower priority than C=O
• Amines with other functional groups are rarely
named as amines

49
Study Check

Give the common name for the following amines.

A. CH3—CH2—NH2

B.

50
Study Check

Give the common name for the following amines.

A. CH3—CH2—NH2 This has one ethyl

group attached to the
nitrogen atom:
ethylamine.
B.
This aromatic amine is
called aniline.

51
 Naming Amines, IUPAC
In the IUPAC names for amines, the e in the corresponding alkane name is
replaced with amine.

Amines with a chain of three or more carbon atoms are numbered to show
the position of the —NH2 group and any other substituents.

Chapter 23/52
 Naming Amines, IUPAC
• If there is an alkyl group attached to the nitrogen atom,
the prefix N and the alkyl name are placed in front of the
amine name.
• If there are two alkyl groups bonded to the N atom, the
prefix N is used for each, and they are listed
alphabetically.

Chapter 23/53
Study Check

Give the IUPAC name for the following amine:

Chapter 23/54
Solution

Give the IUPAC name for the following amine:

STEP 1 Name the longest carbon chain bonded

to the N atom by replacing the e of its
alkane name with amine.

Chapter 23/55
Solution
Give the IUPAC name for the following amine:

STEP 2 Number the carbon chain to show the

position of the amine group and other
substituents.

Chapter 23/56
Solution
Give the IUPAC name for the following amine:

STEP 3 Any alkyl group attached to the nitrogen

atom is indicated by the prefix N and the
alkyl name, which is placed in front of the
amine name.

Chapter 23/57
Common Names of Amines
Common names are often used when alkyl groups are not
branched.
• List the names of the alkyl groups bonded to the N atom in
alphabetical order in front of amine.
• Use prefixes di and tri to identify duplicate alkyl
substituents.

CH3 —CH2—NH2 Ethylamine

CH3 —NH—CH3 Dimethylamine

CH3 —N—CH2—CH3

Chapter 23/58
Ethyldimethylamine
CH3
Aromatic Amines
The amine of benzene is named aniline by IUPAC.
• Alkyl groups on the N use the prefix N with the alkyl name.

HN CH3 H—N—CH3 NH2

Cl
N-methylaniline aniline 3-chloroaniline

Chapter 23/59
• Aniline is used to make many dyes, which give color to
wool, cotton, and silk fibers as well as blue jeans.
Study Check

Give the common name for each amine and classify it as

primary, secondary, or tertiary.

A. CH3—CH2—CH2—NH2

CH3
B. CH3 —CH2—N—CH3

Chapter 23/60
Solution

Give the common name for each amine and classify it as

primary, secondary, or tertiary.

A. CH3—CH2—CH2—NH2 propylamine, 1°

CH3
B. CH3 —CH2—N—CH3 ethyldimethylamine, 3°

Chapter 23/61
Study Check

Give the common name of each amine compound.

CH3
A. CH —CH —N—CH —CH
3 2 2 3

B.
H—N—CH2—CH3

Chapter 23/62
Solution

Give the common name of each amine compound.

CH3
A. CH3 —CH2—N—CH2—CH3 diethylmethylamine

B. H—N—CH2—CH3 N-ethylaniline

Chapter 23/63
Reactions of Amines
• The critical feature of amines is the basic/nucleophilic
lone pair on nitrogen

• In molecules where nitrogen is conjugated with a π system (e.g.,

arylamines, amides), the Lewis basicity of nitrogen can be
transferred to other atoms

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64
Reactivity of Amines

65
 Amines are Bases and Nucleophiles

A base shares its lone pair with a proton.

A nucleophile shares its lone pair with an atom other than a proton.

66
 Amines React as Nucleophiles

a nucleophilic substitution reaction

67
 Amines React as Nucleophiles
nucleophilic addition–elimination reactions

a conjugate addition reaction

68
 This Amine Reacts as a Nucleophile
and as a Base

a nucleophilic addition–elimination reaction

69