ORGANIC CHEMISTRY - CLASS XI

ALDEHYDES
AND
KETONES
Presented by Rusman, M.Si
ALDEHYDES AND KETONES OUTLINE

Definition and
Structure
Nomenclatur
e Isomers

Properties
Preparation
Interesting Aldehydes and
Ketones
 DEFINITION AND STRUCTURE

Aldehyde Ketones
s
Contain the carbonyl group bonded Contain the carbonyl group bonded
to at least one hydrogen atom to two carbon atoms
 NOMENCLATURE ALDEHYDES
IUPAC COMMON
Find the longest continuous chain
that includes the carbonyl carbon
Parent Chain

Change ending “e” with “al”

Number the parent chain assuming

the carbonyl carbon is C-1

Identify substituents on the parent

chain
Position of Alkyl/ Substituent:
C2=α, C3=β, C4=γ, C5=δ, C6=ε
 NOMENCLATURE ALDEHYDES

Formaldehyde Acetaldehyde Propionaldehyde Butyraldehyde

(Methanal) (Ethanal) (Propanal) (Butanal)

CH3 O
CH3 CH2 CH CH2 C H
 NOMENCLATURE
ALDEHYDES
Ʃ C CARBOXYLIC ACID PARENT CHAIN OF NO HAND PRONUNCIATION
ALDEHYDE C WRITTEN
1 Formic acid Formaldehyde 1 - -
2 Acetic acid Acetaldehyde 2  Alpha
3 Propionic acid Propionaldehyde 3  Betha
4 Butyric acid Butyraldehyde 4  Gamma
5 Valeric acid Valeraldehyde 5  Delta
6 Caproic acid Caproaldehyde 6  Epsilon
7 Enanthic acid Enanthaldehyde 7  Zeta
8 Caprylic acid Caprylaldehyde 8  Eta
9 Pelargonic acid Pelargonaldehyde 9  Theta
10 Capric acid Capraldehyde 10  Iota
12 Lauric acid Lauraldehyde 11  Kappa
14 Miristic acid Miristaldehyde 12  Lambda
16 Palmitic acid Palmitaldehyde 13  Mu
18 Stearic acid Stearaldehyde 14  Nu
 NOMENCLATURE KETONES
IUPAC COMMON
Find the longest continuous chain Alkyl alkyl ketone
that includes the carbonyl carbon

Alphabtically
Change ending “e” with “one”

Number the parent chain, C-1 is the Dialkyl ketone

nearest to carbonyl carbon
The same alkyls

Identify substituents on the parent

chain
NOMENCLATURE KETONES

/Hexan-3-one
Ethyl propyl ketone
 ISOMERS OF ALDEHYDES AND KETONES

ALDEHYDES KETONES
1 1
FUNCTIONAL ISOMER FUNCTIONAL ISOMER

2 2
CHAIN ISOMER POSITION ISOMER

3
CHAIN ISOMER
 ISOMERS OF ALDEHYDES AND KETONES

1 FUNCTIONAL ISOMER
 ISOMERS OF ALDEHYDES AND KETONES

2 POSITION ISOMER

No position isomer

3-Pentanone 2-Pentanone

C5H10O
 ISOMERS OF ALDEHYDES AND KETONES

3 CHAIN ISOMER

O
O

C4H8O
H
H

2-Pentanone
Butanal 2-methylpropanal 3-Methyl-2-butanone
C5H10O
 PROPERTIES OF ALDEHYDES AND KETONES
The carbonyl group

Carbonyl groups are strongly polarized,

with a partial positive charge on carbon
and partial negative charge on oxygen

Polarity of carbonyl group contributes

to its reactivity.

C=O bond is shorter, stronger, and

more polar than C=C bond in alkenes
Local trigonal
planar The local geometry around the carbonyl
geometry group is trigonal planar

Bond angles are about 120o around the

carbon atom
 PROPERTIES OF ALDEHYDES AND KETONES
Physical Properties

Number of C Aldehyde Ketone

C1-C2 Gas -
Phase C3-C11 Liquid Liquid
> C11 Solid Solid

Water Solubility
Aldehydes and
Ketones have
significant water
solubility.
 PROPERTIES OF ALDEHYDES AND KETONES
Physical Properties
Boiling point
For compounds of comparable molecular weight.
Alkanes, ethers < aldehydes, ketones < alcohols < carboxylic acids

Dispersion Dipole-dipole Hydrogen Bonding

Forces
 PROPERTIES OF ALDEHYDES AND KETONES
Physical Properties
Boiling point
 PROPERTIES OF ALDEHYDES AND KETONES
Chemical Properties

1 Reduction of Aldehydes and Ketones

2 Oxidation of Aldehydes and Ketones

Mild Oxidator
Strong Oxidator
a. Oxidation with Tollens’ reagent
a. Oxidation with Na2Cr2O7 b. Oxidation with Fehling’s reagent
b. Oxidation with K2Cr2O7 c. Oxidation with Benedict’s reagent
d. Oxidation with Luff-Schoorl

3 Addition of Aldehydes and Ketones

a. Addition of hydrogen cyanide

b. Addition of sodium bisulphite
c. Addition of Grignard reagents
d. Addition of Alcohols
 PROPERTIES OF ALDEHYDES AND KETONES
1 Reduction of Aldehydes and Ketones

O O H O O H
re d re d
R C H R C H R C R R C R

H H
A d e h y d e s P rim a ry A lc o h o ls A d e h y d e s S e c o n d a ry A lc o h o ls

O O H
O
N i H C C H O H
H 3 C C H + H 2 3 2 N i H C C H C H 3
H 3 C C C H 3 + H 2 3
E th a n a l E th a n o l
P ro p a n o n e P ro p a n -2 -o l

Reductor
a. H2, Ni
b. Lithium aluminium hydride (LiAlH4),
c. Sodium borohydride (NaBH4)
 PROPERTIES OF ALDEHYDES AND KETONES
2 Oxidation of Aldehydes and Ketones

Oxidator
a. K2Cr2O7/ H+
b. KMnO4/ H+

Milder oxidizing agents:

a. Tollens’ reagent
b. Fehling’s reagent Tests that have been developed to
c. Benedict’s solution determine the presence of aldehydes
d. Luff-Schoorl
 PROPERTIES OF ALDEHYDES AND KETONES
a. Oxidation with Tollens’ reagent
Tollens’ reagent is a solution of silver nitrate in ammonium hydroxide (actually
Ag(NH3)2OH). Aldehyde form silver precipitate (silver mirror) with Tollens’
reagent. Ketones do not react
O O
NH 3, H 2O
R C H + Ag2O R C OH + Ag
warm
an aldehyde a carboxylic acid silver metal

b. Oxidation with Fehling’s reagent

Fehling solution is an alkaline solution of cupric ion complexed with sodium

potassium tartrate. Aldehyde form red precipitate with Fehling’s solution.
Ketones and aromatic aldehydes do not react.
O O
NH 3
R C H + CuO R C OH + Cu2O
an aldehyde blue red
solution a carboxylic acid precipitate
 PROPERTIES OF ALDEHYDES AND KETONES

c. Oxidation with Benedict’s reagent

Benedict’s solution is an alkaline solution of cupric ions complexed with sodium
potassium citrate ions. It reacts in the same way as Fehling’s solution.

O O
NH 3
R C H + CuO R C OH + Cu2O
an aldehyde blue red
solution a carboxylic acid precipitate

d. Oxidation with Luff-Schoorl

CuSO4, NaOH, and Citric acid (CuO)
O O
NH 3
R C H + CuO R C OH + Cu2O
an aldehyde blue red
solution a carboxylic acid precipitate
 PROPERTIES OF ALDEHYDES AND KETONES
3 Addition of Aldehydes and Ketones
a. Addition of hydrogen cyanide

ALDEHYDES KETONES

Cyanohydrin(Alkyl alkane nitrile) are formed

δ-
O OH
C
+
+ HCN C
δ
CN
cyanohydrin

O OH O OH
H3 C C H + HCN H 3C C H H3 C C CH3 + HCN H 3C C CH 3
CN Acetone CN
acetaldehyde
acetaldehyde Acetone
cyanohydrin cyanohydrin
 PROPERTIES OF ALDEHYDES AND KETONES
b. Addition of sodium bisulphite

ALDEHYDES KETONES

Aldehyde and methyl ketones react with saturated aqueous solution of sodium bisulphite
(sodium hydrogen sulfonate) to form solid addition compounds.

δ-
O ONa OH
C + NaSO3H C C
δ+
SO3H SO3 Na
addition
compound

O OH
O OH
H3C C H + NaHSO3 H 3C C H
H3C C CH3 + NaHSO3 H3C C CH3
acetaldehyde SO3Na SO3Na
Acetone
acetaldehyde
bisulphyte Na-hydroxypropanesulfonate
Acetone bisulfite
 PROPERTIES OF ALDEHYDES AND KETONES
c. Addition of Grignard reagents

ALDEHYDES KETONES

O OMgX OH
H2O
C + R MgX C C + MgX(OH)
H+
R R
Aldehyde Grignard Addition Alcohol
or ketone reagent compound

O OMgX OH
H 2O
H C H + RMgX H C H H C H
H+ OMgX OH
R R O
H2O
Formaldehyde 1O Alcohol H3C C CH3 + RMgX H3C C CH3
H+
H3C C CH3
R R
Acetone O
3 Alcohol
O OMgX OH
H2O
H3C C H + RMgX H3 C C H H 3C C H
H+
R R
Acetalldehyde O
2 Alcohol
 PROPERTIES OF ALDEHYDES AND KETONES
c. Addition of Alcohols
ALDEHYDES KETONES
Acid catalyst
aldehyde or ketone + alcohol → hemiacetal
Acid catalyst
hemiacetal + alcohol → acetal
− +

+
−

aldehyde alcohol
hemiacetal

− +

+
−

ketone alcohol
hemiacetal

A hemiacetal is an organic compound that possesses a carbon atom that is bound to

an OH (hydroxy) group and an OR (alkoxy) group
 PREPARATION OF ALDEHYDES AND KETONES

1 1
Oxidation of 1OAlcohols Oxidation of 2OAlcohols

2 2
Catalytic dehydrogenation of 1O Alcohols Catalytic dehydrogenation of 2O Alcohols

3 3
Ozonolysis of alkenes Ozonolysis of alkenes

4 4
Hydration alkynes Hydration alkynes
5 5
Alkaline hydrolysis of gem-dihalides Alkaline hydrolysis of gem-dihalides

6
Friedel-Craft Acylation
 PREPARATION OF ALDEHYDES AND KETONES

1 Oxidation of 1OAlcohols Oxidation of 2OAlcohols

OH O OH O

(O ) (O)
R C H R C H R C H R C R'

H R'

OH O
OH O
(O ) (O)
H3C C H H3C C CH3
H 3C C H H 3C C H

CH3
H

Oxidizing agents:
K2Cr2O7/H+ or KMnO4/H+
Pyridinium dichromate (PDC): (C5H5NH)2Cr2O7
 PREPARATION OF ALDEHYDES AND KETONES

2 2
Catalytic dehydrogenation of 1O Alcohols Catalytic dehydrogenation of 2O Alcohols
OH O
O
Cu Cu
CH 3CH2OH + H 3C C H H3C C H H3C C CH3
300oC 300oC
ethanol
acetaldehyde CH3

3 3
Ozonolysis of alkenes Ozonolysis of alkenes
 PREPARATION OF ALDEHYDES AND KETONES

4 Hydration alkynes 4 Hydration alkynes

H O
HgSO4
H C C H + H OH H C C H H C CH3
H2SO 4
acetylene O acetaldehyde
H

5 Alkaline hydrolysis of gem-dihalides 5 Alkaline hydrolysis of gem-dihalides

Cl OH Cl OH
O O
H2O - H2O H2O - H2O
H3C C Cl H3C C OH CH3 C H H3C C CH3 H3C C CH3
NaOH CH3 C CH3
NaOH
H H Acetaldehyde Cl Propanone
OH
unstable unstable
 PREPARATION OF ALDEHYDES AND KETONES

6 Friedel-Craft Acylation
O O
Lewis acid
Ar + RCOCl or Ar'COCl Ar C R or Ar C Ar'
Examples:

O
O C CH3
+ H3C AlCl3
C Cl
+ HCl

O O
C Cl C
+ AlCl3
+ HCl
INTERESTING ALDEHYDES AND KETONES
Aldehydes are often recognizable by their “sweet”
smells
INTERESTING ALDEHYDES AND KETONES
INTERESTING ALDEHYDES AND KETONES

Acetaldehyde (CH3CHO): Sweet smelling.

Present in ripe fruits, especially in apples.

Formaldehyde, HCHO
INTERESTING ALDEHYDES AND KETONES

D-Glucose
INTERESTING ALDEHYDES AND KETONES
Some ketones (e.g. acetone) have a “sweet” smell
also).
INTERESTING ALDEHYDES AND KETONES
INTERESTING ALDEHYDES AND KETONES

Testosterone
Male sex hormone

Progesterone Female sex hormone

Cortisone
Adrenal hormone
THANK YOU!