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KIM3203

KIMIA SEBATIAN KARBONIL


(CARBONYL COMPOUND
CHEMISTRY)
CHAPTER 1
ALDEHYDES AND KETONES

DR. SORAYA SHAFAWATI BINTI MOHAMAD


TAHIER

Tugasan dan Ujian = 60%


(Tugasan : Kuiz, Latihan, Pembentangan
berkumpulan = 30 %)
(Ujian = 30%)
Peperiksaan Akhir = 40%

Course Outline
1.1 Structures of Aldehydes and Ketones
1.2 Naming Aldehydes and Ketones
1.3 Bonding and Physical Properties
1.4 Chemical Properties of Aldehydes and
Ketones

1.1
Structure of Aldehydes and Ketones
A carbonyl group (C=O)
 In an aldehyde is
attached to at least
one H atom.


In a ketone is attached
to two carbon groups.

Structure of Aldehydes and Ketones


Aldehydes (i.e. RCHO)
Carbonyl
group

Ketone (i.e R2CO / CO)


O

R = Alkyl or Aryl
group

sp2
2-pentanone

pentanal
O

Structure of Aldehydes and Ketones

Two structural features determine the chemistry and


properties of aldehydes and ketones.

Making it relatively
uncrowded

Reactions of Aldehydes and Ketones


React with nucleophiles
R groups around the carbonyl carbon
increases, the reactivity of the carbonyl
compound decreases.

1.2
Nomenclature of Aldehydes
Guidelines:Aldehyde as parent (suffix - al)

Identify the longest chain

Nomenclature of Aldehydes
Aldehyde carbon is assigned as number 1, despite
the presence of alkyl substituents, pi bond or
hydroxyl groups

CORRECT

INCORRECT!!

 Number the chain or ring to put the CHO group


at C1, but omit this number from the name.

Common Names of Aldehydes


Many simple aldehydes have common names that are
widely used.
A common name for an aldehyde is formed by taking the
common parent name and adding the suffix aldehyde.

Greek letters are used to designate the location of


substituents in common names.

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Nomenclature of Aldehydes
Dialdehydes are compounds that contain two
aldehyde groups. They are named by adding the
suffix dial to the corresponding hydrocarbon
name.
 For example a molecule with four carbons and
two aldehyde groups is called butanedial.


Nomenclature of Ketones
In the IUPAC system, all ketones are
identified by the suffix one.
Find the longest continuous chain
containing the carbonyl group, and
change the e ending of the parent alkane
to the suffix -one.
Number the carbon chain to give the
carbonyl carbon the lowest number.

Nomenclature of Ketones

For ketones are formed by naming both alkyl


groups on the carbonyl carbon, arranging them
alphabetically, and adding the word ketone.

Naming Ketones and Acyl Groups

Sometimes, acyl groups must be named as substituents.


The three most common acyl groups are shown below:

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Examples
Cl
5

O
4-Chloro-2,2-dimethylpentanal

Br
1

O
6-Bromo-4-ethyl-3-heptanone

CO2H O
H

2-Methanoylbenzoic acid
(o-formylbenzoic acid)

SO3H

O
4-Ethanoylbenzenesulfonic acid
(p-acetylbenzenesulfonic acid)

1.3
Physical Properties

Physical Properties
 The

polar carbonyl group


 Provides dipole-dipole interactions.
+ + C=O
C=O
Does not have H on the oxygen atom.
 Cannot form hydrogen bonds.


THE CARBONYL GROUP IS PLANAR


(SP2 HYBRIDIZED)

Nu:
.

.
..

O ..

Nu:
nucleophiles can attack from either top or bottom

Physical Properties

Boiling Points
Aldehydes and ketones have
 Polar carbonyl groups (C=O).
+ C=O
 Attractions between polar groups.
+ + C=O
C=O
 Higher boiling points than alkanes and ethers of
similar mass.
 Lower boiling points than alcohols of similar mass.

Physical Properties
Comparison of Boiling Points

Physical Properties


Solubility in water

The electronegative O atom of the carbonyl


group in aldehydes and ketones forms
hydrogen bonds with water.

Spectroscopic PropertiesIR Spectra


Aldehydes and ketones exhibit a strong peak at
~1700 cm1 due to the C=O.
The sp2 hybridized CH bond of an aldehyde shows
one or two peaks at ~2700 2830 cm1.

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IRCarbonyl Absorption
Most aldehydes have a carbonyl peak around 1730 cm1,
whereas for ketones, it is typically around 1715 cm1.
Ring size affects the carbonyl absorption in a predictable
manner.

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IRConjugation Effects
Conjugation leads to a somewhat weaker C=O bond, thus
shifting the carbonyl absorption to longer wavelengths.

The effect of conjugation on


the carbonyl absorption
in an IR spectrum

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1H

and 13C NMR absorptions

The sp2 hybridized CH proton of an aldehyde is highly


deshielded and absorbs far downfield at 910 ppm.
Splitting occurs with protons on the carbon, but the
coupling constant is often very small (J = 13 Hz).
Protons on the carbon to the carbonyl group absorb
at 22.5 ppm.
Methyl ketones, for example, give a characteristic
singlet at ~2.1 ppm.
In a 13C NMR spectrum, the carbonyl carbon is highly
deshielded, appearing in the 190215 ppm region.
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1H

NMR of Propanal

There are three signals due to the three different kinds


of Hydrogens, labeled Ha, Hb, and Hc.
The deshielded CHO proton occurs downfield at 9.8
ppm.
The Hc signal is split into a triplet by the adjacent CH2
group, but the coupling constant is small.
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13C

NMR absorptions

There are three signals due to the three different kinds of


carbons, labeled Ca, Cb, and Cc.
The deshielded carbonyl carbon absorbs downfield at
203 ppm.
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