CHM557

ORGANIC
CHEMISTRY
CHAPTER 1
ALDEHYDES AND
KETONES I:
OXIDATION,
REDUCTION AND
SYNTHESIS
 COURSE LESSON PLAN
At the end of the chapter, student should be able to
understand
 Introduction to carbonyl compounds
 Nomenclature of aldehydes and ketones
 Physical properties of aldehydes and
ketones
 Reduction of aldehydes and ketones
 Synthesis of aldehydes and ketones
 Tests for aldehydes and ketones
INTRODUCTION TO
CARBONYL
COMPOUNDS
 The Carbonyl Group
 The carbonyl group consists of
 one s bond formed by the overlap of sp2 hybrid orbitals,
and
 one p bond formed by the overlap of parallel 2p orbitals
 Carbonyl
Compounds
 Structure of Aldehydes
 The functional group of an aldehyde is a carbonyl
group bonded to a H atom
 in methanal, it is bonded to two H atoms
 in all other aldehydes it is bonded to one H and one
carbon atom

H H
C O C O
H H3 C
Methanal Ethanal
(formaldehyde) (acetaldehyde)
 Structure of Ketones

 The functional group of a ketone is a carbonyl group

bonded to two carbon atoms

O O
CH3 -C-CH3
Propanone Cyclohexanone
(Acetone)
NOMENCLATURE OF
ALDEHYDES AND
KETONES
 Naming
Aldehydes
 IUPAC NAMES OF ALDEHYDES

The IUPAC names of aldehydes are obtained by

dropping the –e and adding -al to the name of
the parent hydrocarbon.

butane al
butanal
The parent hydrocarbon is the longest chain that
carries the –CHO group.

This chain has 4

carbon atoms

3 2

1
4
The parent hydrocarbon is the longest chain
that carries the –CHO group.

This chain has 5

carbon atoms

5 4 3 2

1
The –CHO group is always at the beginning of
the carbon chain. The carbonyl carbon is
numbered as carbon 1.

5 4 3 2

3-methylpentanal
 For unsaturated aldehydes, show the
presence of the C=C by changing the infix -
an- to -en-

O
2-Pentenal or pent-2-enal
 COMMON NAMES OF ALDEHYDES

• The common names of aldehydes are derived from the

common names of the carboxylic acids.
• The –ic acid or –oic acid ending of the acid name is
dropped and is replaced with the suffix –aldehyde.

butyric acid butyraldehyde

 NOMENCLATURE OF CYCLIC ALDEHYDES
 Aliphatic aldehydes containing a ring as well as aromatic
aldehydes in which the aldehyde (-CHO) group is attached
directly to the benzene ring are named by adding suffix
carbaldehyde to the name of the corresponding hydrocarbon.

CHO
CHO
56 1
4 2
3
CH3
cyclohexanecarbaldehyde 2-methylcyclohexanecarbaldehyde

O
C H

2-cyclopentenecarbaldehyde
 NOMENCLATURE OF AROMATIC COMPOUNDS
CHO
CHO

NO2
benzaldehyde 4-nitrobenzaldehyde

If the aldehyde group is not attached directly to the

benzene ring, the aldehyde is named as an aryl derivatives
of the corresponding aldehyde.

3 2 1
CH2CHO CH=CHCHO

phenylethanal 3-phenylpropenal
Naming
Ketones
 IUPAC NAME OF KETONES
 The IUPAC name of a ketone is derived from the
name of the alkane corresponding to the longest
carbon chain that contains the ketone-carbonyl
group.
 The parent name is formed by changing the –e
ending of the alkane to -one.

propane propanone
one
 If the carbon chain is longer than 4 carbons, the chain is
numbered. Numbering is begin from the carbon which
closest to the C=O so that the carbonyl carbon has the
smallest number possible, and this number is prefixed to
the name of the ketone.

This end of the chain is closest to the C=O.

Begin numbering here.
1 2 3 4 5 6

IUPAC name: 3-hexanone

New IUPAC name: hexan-3-one
 Examples:

O O O O
CH3CH2CCH2CH2CH2 CH3CH CHCH2CCH3 CH3CH2CCH2CCH3

3-hexanone 4-hexen-2-one 2,4-hexanedione

 COMMON NAME OF KETONES
The common names of ketones are derived by naming
the alkyl or aryl groups attached to the carbonyl
carbon followed by the word ketone.

ethyl propyl

ethyl propyl ketone

IUPAC nomenclature and common names for aldehyde
and ketone compounds

Compound Structure formula IUPAC Common name

nomenclature
Aldehyde H2C=O Methanal Formaldehyde

CH3CH=O Ethanal Acetaldehyde

CH3CH2CH=O Propanal Propionaldehyde

CH3CH2CH2CH=O Butanal Butyraldehyde

Ketone CH3COCH3 Propanone Acetone

CH3CH2COCH3 2-butanone Methyl ethyl ketone

CH3CH2CH2COCH3 2-pentanone n-Propyl methyl ketone

CH3CH2COCH2CH3 3-pentanone Diethyl ketone

 NOMENCLATURE OF CYCLIC KETONES AND AROMATIC
COMPOUNDS
 The parent name is formed by changing the –e ending of the
cycloalkane to -one.
 Carbonyl carbon is designated C1.
O
O
612
5 3
4

CH3
cyclohexanone 4-methylcyclohexanone

 Aromatic compound:
- phenyl is used as part of the name.

O O
C CH3 C

phenylethanone diphenylmethanone
 NAME AS SUBSTITUENT
o A ketone or aldehyde group can also be named as a substituent
on a molecule with a higher priority functional group.
o The ketone carbonyl is designated by the prefix oxo-.
o The –CHO group is named as a formyl group.
o Aldehyde priority is higher than ketone.

O
O O 3
C H
4
2
CH3CH2 C CH2 C H 5
5 4 3 2 1
6
1 COOH

3-oxopentanal 2-formylbenzoic acid

O O
CH3 C CH2 C OH
4 3 2 1
3-oxobutanoic acid
 MAIN GROUPS

Acids
Esters
Aldehydes
Ketones
decreasing priority Alcohols
Amines
Alkenes
Alkynes
Alkanes
Ethers
Halides
 PHYSICAL
PROPERTIES OF
ALDEHYDES AND
KETONES
Oxygen is more electronegative than carbon (3.5 vs 2.5)
and, therefore, a C=O group is polar
- aldehydes and ketones are polar compounds and interact in
the pure state by dipole-dipole interaction
- they have higher boiling points and are more soluble in
water than nonpolar compounds of comparable molecular
weight

+ -
C O
 PHYSICAL PROPERTIES OF ALDEHYDES AND
KETONES
1. BOILING POINTS
Boiling points for ketones and aldehydes are higher than
hydrocarbons and ethers of similar molecular weights.
- Reason: Polarization of the carbonyl group creates dipole-
dipole attractions between the molecules of ketones and aldehydes.

This attractions resulting in higher boiling points for ketones and

aldehydes.

Boiling points of ketones and aldehydes are lower than alcohols of

similar molecular weight.
- Reason: Ketone and aldehyde did not have O-H and N-H bonds.
Thus, these compounds can not form hydrogen bonds with each
other. They rely only on intermolecular dipole-dipole interactions.
 Boiling points of alkane, ether, aldehyde, ketone and
alcohol of similar molecular weight

O O

CH3CH2CH2CH3 CH3 O CH2CH3 CH3CH2 C H CH3 C CH3 CH3CH2CH2-OH

butane methoxyethane propanal acetone 1-propanol
o
bp 0oC bp 8oC bp 49oC bp 56 C bp 97oC
2. WATER SOLUBILITIES
o Ketones and aldehydes have lone pairs of electrons and can act
as hydrogen bond acceptors with other compounds having O-H
or N-H bonds.
o For example, the –OH hydrogen of water or an alcohol can
form a hydrogen bond with unshared electrons on a carbonyl
oxygen atom.

R R δ+ δ-
δ+ δ- C O
C O δ+
R' δ+ δ+ H δ+
H H R
H O
O δ-
hydrogen bonding δ- hydrogen bonding
o Because of the hydrogen bonding, ketones and aldehydes are
good solvents for polar hydroxylic substances such as alcohols.

o Ketones and aldehydes are soluble in water.

- ketones and aldehydes having ≤ 5 carbons are H2O soluble
because they can hydrogen bond with H2O.

- ketones and aldehydes having more than 4 carbon are H2O

insoluble because the nonpolar alkyl portion is too large to
dissolve in the polar H2O solvent.

- the solubility of ketones and aldehydes in water decreases

with the increasing length of the carbon chain.
 REDUCTION OF
ALDEHYDES AND
KETONES
 Reduction of Aldehydes and
Ketones

Deoxygenation of aldehydes
Reduction to alcohol and ketones

Aldehydes reduced to 1° alcohols C=O group reduced

Ketones reduced to 2° alcohols to a -CH2- group

Reagents: Methods:
Catalytic hydrogenation Clemmensen reduction
Metal Hydride Reduction Wolff–Kishner reduction
Reduction of Aldehydes and Ketones
Reduction to alcohol

Deoxygenation of aldehydes and ketones

O H H
deoxygenation
R C H R C H
aldehyde methylene group

O H H
deoxygenation
R C R' R C R'
ketone methylene group
REDUCTION
TO
ALCOHOL
 Mechanism of hydride reduction of
a carbonyl group
 The mechanism involves:
i. Addition of nucleophilic hydride ion, H-, to the positively
polarized electrophilic carbon of C=O to form an alkoxide ion
intermediate
ii. Protonation of the alkoxide ion intermediate
 1. CATALYTIC
HYDROGENATION
 Reducing a ketone or an aldehyde to an alcohol involves adding 2
hydrogen atoms across the C=O.

 Catalytic hydrogenation:
- Add H2 with Raney nickel catalyst.
- Also reduces any C=C bonds.
- Raney nickel is finely divided Ni powder saturated with hydrogen
gas. It will attack the alkene first, then the carbonyl.

O
OH
Raney Ni
C + H2 C
H
 Examples:
OH
O
Raney Ni
H3C C H
H3C C H + H2
H
ethanal (aldehyde) ethanol (primary alcohol)

O OH
Raney Ni
+ H2

cyclohexanone cyclohexanol
(ketone) (secondary alcohol)

O OH
Raney Ni
+ H2
 2. Metal Hydride Reduction

o The most common laboratory reagents for the

reduction of aldehydes and ketones are NaBH4 and
LiAlH4.
o Both reagents are sources of hydride ion, H:-, a very
powerful nucleophile.

H H
+
Na H-B-H Li + H-Al-H H

••
H H
Sodium Lithium aluminum Hydride ion
borohydride hydride (LAH)
 2a. Sodium Borohydride
(NaBH4)

 NaBH is not sensitive to moisture and a source of hydrides

4
(H-).

 The reactions takes place in alcohols, ethers and water.

 ONLY REACTS with carbonyl of aldehyde or ketone, NOT with

carbonyls of esters or carboxylic acids.

 DO NOT reduce carbon-carbon double bonds.

 It adds the equivalent of “ H- ”

2a. Sodium Borohydride
(NaBH4)

1. NaBH4 / ethanol
2. H3O+

1. NaBH4 / ethanol
2. H3O+
 Mechanism of NaBH4 Reduction
 The key step in metal hydride reduction is transfer of a hydride ion to
the C=O group to form a tetrahedral carbonyl addition compound
(alkoxide ion).
 Protonation of the intermediate with dilute acid to form alcohols.

1. Hydride attacks the carbonyl carbon, forming an alkoxide ion

+
H O O Na
Na+ H B H R C R' R C R' BH3
H H

Alkoxide ion
2. Protonation by dilute acid to form alcohol
Na+ O O H
R C R' H O H R C R' H O H
H H H
 2b. Lithium Aluminium Hydride(LiAlH 4 or
LAH)
o LiAlH4 is source of hydrides (H-)
o Stronger reducing agent than NaBH4, but dangerous to work
with.
o Reduces ketones and aldehydes into the corresponding
alcohol.
o Converts esters and carboxylic acids to 1o alcohols.
o LiAlH4 has NO EFFECT on the benzene ring or the double bond.
o Like NaBH4, it adds the equivalent of “ H- ”.
o Unlike NaBH4, LiAlH4 reacts violently with water, methanol,
and other protic solvents. Reductions using it are carried out in
diethyl ether or tetrahydrofuran (THF).
 O OH
1. LiAlH4, ether
C +
C
2. H3O
aldehye or ketone H
alcohol

O OH
1. LiAlH4, ether
R C OR' R C H
2. H3O+
ester H
primary alcohol

O OH
1. LiAlH4, ether
R C OH R C H
2. H3O+
carboxylic acid H
primary alcohol
 Examples
CH3 O CH3 OH
1. LiAlH4, ether
H3C C CH2 C H H3C C CH2 C H
2. H3O+
CH3 CH3 H

O H OH
1. LiAlH4, ether
2. H3O+

O OH
1. LiAlH4, ether
OCH3 2. H3O+
H
H
Comparison of Reducing
Agents

 LiAlH4 is stronger.
 LiAlH4 reduces more
stable compounds
which are resistant to
reduction.
NaBH4 is more selective
 COMPARISON BETWEEN CATALYTIC REDUCTION
AND METAL HYDRIDE REDUCTION
 Metal hydride reducing agents DO NOT normally reduce
carbon-carbon double bonds.

OH O OH

1.NaBH
NaBH
44
H2, Raney Ni
2. H3O+

1. LiAlH4, ether
C=C reduce
C=C does not reduced 2. H3O +
to –CH2-

OH

NaBH
C=C4 does not reduced
 REDUCTION REACTIONS OF CATALYTIC
HYDROGENATION, NaBH4 and LiAlH4
H2, Raney Ni NaBH4 LiAlH4
Aldehyde O OH OH OH

R C H R C H R C H R C H
H H H
Ketone
OH OH OH
O
R C R' R C R' R C R'
R C R'
Alkene H No reaction
H No reaction
H
H H
C C
C C
Acid anion No reaction No reaction
OH
O
R C H
Ester R C O No reaction No reaction
H

O OH
R C H
R C OR'
H
Note: The products shown are the final products, after hydrolysis of the alkoxide.
 Exercise
Determine the structure of products or reagents or starting compounds that
would complete the following reactions.
O

i)LiAlH4/ether OEt H2/Raney Ni

A B
ii)H3O+

O
i)NaBH4 (excess)/ MeOH
H
C
ii)H3O+

O D O E HO

HO HO

OH
F i) LiAlH4/ether
ii) H3O+
DEOXYGENATIO
N OF
ALDEHYDES
AND KETONES
 REMOVAL OF CARBONYL
GROUP : DEOXYGENATION
 Deoxygenation: Replacement of the C=O of a
ketone or aldehyde with two hydrogen atoms.
 C=O to -CH2-

 Two methods:
i. Clemmensen reduction if molecule is stable in hot
acid.
ii. Wolff-Kishner reduction if molecule is stable in
very strong base.
 i. Clemmensen Reduction
Refluxing an aldehydes or ketones with amalgamated zinc (zinc
treated with mercury salts) in aqueous HCl converts the carbonyl
group to a methylene group.

O
Zn(Hg)
R C H R CH2 H
aldehyde aq HCl alkane

• Examples:
O
Zn(Hg)
CH3CH2CH2 H
CH3CH2CH
HCl, H2O propane
propanal

O H
Zn(Hg)
C H
H
aq HCl H
benzaldehyde
toluene
• The substrate must be tolerant of the strongly acidic conditions of
the Clemmensen reduction. Acid-sensitive substrates should be
reacted in the Wolff-Kishner reduction, which utilizes strongly
basic conditions.

• Substituents (examples, hydroxyl, alkoxyl & halogens) at alpha

position of the carbonyl group are labile. The substituents are
reduced first followed by the reduction of the resulting
unsubstituted aldehyde or ketone to the parent hydrocarbon.

• Clemmensen reduction might give a dehydration by-products by

the acid catalyzed reaction.
 ii. Wolff-Kishner Reduction
o The aldehyde or ketone and hydrazine are refluxed with KOH
or potassium tert-butoxide in a high-boiling solvent.

o High-boiling solvent: ethylene glycol, diethylene glycol, or

DMSO.

o A molecule of nitrogen is lost in the last steps of the reaction.

O NNH2 H H
H2N NH2 C KOH H2O
C H2O C N2
heat
 ii. Wolff-Kishner Reduction
O NNH2 H H
N2H4 KOH, heat
diethylene glycol N2 H2O

propiophenone hydrazone n-propylbenzene (82%)

or
O
H H
(1) N2H4
N2 H2O
(2) KOH, heat
propiophenone n-propylbenzene (82%)

O NNH2 H
t-BuO K
H2N NH2 H N2
DMSO, a solvent

O
H H
(1) N2H4
OH N2 H2O
OH (2) KOH, heat
 Mechanism of Wolff-Kishner Reduction
Step 1: Formation of imine

O O H O H O H
R C R' R C R' H R C R'
H2N N H H2N N H
H2N NH2 H
H O H

H
O H H O H R C R' R C R'
R C R' R C R' H2N N H2N N H
H2N N H H2N N H H
minor major

R C R' R C R'
H2N N H H2N N H3O+

H2O
 Step 2: Wolff-Kishner Reduction

R' H
OH R' R'
C N N C N N C N N
R H R H R H

R' R'
C N N H O H H C N N OH
R H R H

R' R' R'

H C N N OH H C N N H C N N
R H R R (N2)

R' R'
H C H O H H C H OH
R R
product
 Exercise
Provide the products/reagent for the following reactions.
1. O
(1) N2H4
?
(2) KOH, heat
OH

2. O
Zn(Hg)
?
aq HCl
OH

3. O (1) N2H4
?
(2) KOH, heat

4.
?
OH
H OH
O
SYNTHESIS OF ALDEHYDES
AND KETONES
Synthesis of aldehydes
1. Reduction of acid chlorides and esters
2. Oxidation:
i. Oxidation of primary alcohols
ii. Oxidation cleavage of alkenes by
ozonolysis

Synthesis of ketones
1. Oxidation of secondary alcohols
2. Oxidation cleavage of alkenes by
ozonolysis
SYNTHESIS OF
ALDEHYDES
1. REDUCTION OF ACID CHLORIDES AND
ESTERS
 Reduction to an aldehyde can be accomplished by using a more
reactive carboxylic acid derivatives such as an acyl chloride,
ester or nitrile and a less reactive hydride source.

 The use of a sterically hindered and therefore less reactive

aluminum hydride reagent is important.

 LiAlH4 is a strong reducing agent that reduces acids, acid

chlorides, anhydrides and esters to primary alcohols.

 Acid chlorides and esters are reduced to aldehydes by mild

reducing agents.
 A. REDUCTION OF ACID
CHLORIDES TO
ALDEHYDES

Mild reducing agents i.e. lithium

tri-tert-butoxyaluminum hydride Rosenmund
(LiAl-+H(O-t-Bu)3) and reduction
diisobutylaluminium hydride
(DIBAL-H or DIBAH).
 Mild reducing agents

Lithium tri-tert-butoxyaluminum hydride

LiAl-+H(O-t-Bu)3 is a
weaker reducing agent
than LiAlH4
 Mild reducing agents
Diisobutylaluminium hydride (DIBAL-H)

 A bulky “electrophilic” reducing agent which has two bulky isobutyl

groups which makes this reagent less reactive than LiAlH4.
 Coordinates to its carbonyl host before delivering its hydride.
 It reacts only once with the carbonyl carbon forming a stable
tetrahedral complex which will only fall apart during the workup
procedure. Thus, the carbonyl group will not reduce further to
alcohol.
 REDUCTION OF ESTERS TO
ALDEHYDES
• Esters can be converted to aldehydes using
diisobutylaluminum hydride (DIBAL-H or DIBAH).

• The reaction is usually carried out at -78oC to prevent

reaction with the aldehyde product.

O O
1) DIBAL-H, -78oC, 1 equiv.
R C OR' R C H R' OH
+
2) H3O alcohol
ester aldehyde
Mechanism Reduction of aldehyde from ester using DIBAL-H

1
 Examples:

O 1) DIBAL-H, toluene, -78oC O

OCH3 2) H + H
H3OO
2

Lactones (cyclic esters) are

reduced to lactols
 MILD REDUCING AGENTS
O O
1) LiAl-+H(O-t-Bu)3, ether, -78oC
R C Cl R C H
acid chloride 2) H2O
aldehyde

O O
1) DIBAL-H, -78oC, 1 equiv.
R C Cl R C H
acid chloride 2) H3O+
aldehyde

Examples:

CH3 O CH3 O
1) LiAl-+H(O-t-Bu)3, ether, -78oC
CH3CHCH2C Cl CH3CHCH2C H
2) H2O

O 1) DIBAL-H, -78oC, 1 equiv.

O
Cl 2) H3O+
H

Dry ice (solid CO2) Only 1 equivalent of very cold DIBAL-H is used to
sublimes at –78°C avoid further reduction of the aldehyde to an alcohol
 ROSENMUND REDUCTION (CATALYTIC
HYDROGENATION)

Chemical reaction that reduces an acid chloride to

an aldehyde using hydrogen gas over palladium on
carbon poisoned with barium sulfate – selective
reduction
 2. OXIDATION
1. Oxidation of primary alcohol to aldehydes.

Can use any of these reagents:

• Chromium Based Reagents

i. Sarett reagent: Chromium trioxide added to an excess of

pyridine leads to the formation the CrO3 • 2 Py complex
(Sarett Reagent)

ii. Collins reagent: CrO3 • 2 Py complex diluted in dicloromethane

iii. Pyridinium chlorochromate (PCC) in dichloromethane

 2. OXIDATION
H
O
R C OH Pyridinium chlorochromate (PCC)
CH2Cl2, 25oC
R C H
H aldehyde
o
1 alcohol

H
Cr3O. 2py
O
R C OH
CH2Cl2
R C H
H aldehyde
1o alcohol
Cr3O.2py in CH2Cl2 = Collins reagent

H
Cr3O. 2py O
R C OH
R C H
H aldehyde
1o alcohol
Cr3O.2py = Sarret reagent
 Examples:
H H
C PCC C
OH CH2Cl2 O
H

H H
C PCC C
OH CH2Cl2 O
H

H H
C C
OH CrO3.2py O
H
 PCC Reagents

 PCC is made from chromium trioxide under acidic conditions.

 It is used in organic solvents such as methylene chloride
(CH2Cl2).
 PCC will not fully oxidize a primary alcohol to the carboxylic
acid as does the Jones reagent.
 A disadvantage to using PCC is its toxicity.
2. Oxidation cleavage of alkenes by ozonolysis

 Ozonolysis:
- The reaction of alkenes with ozone (O3) to form an ozonide,
followed by hydrolysis of the ozonide to produce aldehydes
and /or ketone.
- Widely used to determine the position of the carbon-carbon
double bond.
- Ozonolysis is milder and both ketone and aldehydes can be
recovered without further oxidation.

R R' R O R' (CH3)2S R R'

C C O3 C C C O O C
R O O H or H2O, Zn/H+
R H R H
ozonide ketone aldehyde

H+ = acetic acid
 Examples:

H
H
i) O3
CH3 C C CH3 O C CH3
ii) (CH3)2S CH3C O
CH3 ethanal CH3
2-methyl-2-butene (aldehyde)
propanone
(ketone)

H
i) O3 H
CH3CH2 C C CH3 O C CH3
ii) (CH3)2S
CH3CH2 C O
H H
2-pentene propanal ethanal
(aldehyde) (aldehyde)

* (CH3)2S can be replaced with H2O and Zn/H+

 Exercise
Provide the products/reagent for the following reactions. Include
intermediate(s) where necessary.

1. O
1) DIBAL-H, toluene, -78oC
O ?
+
2) H3O

2. OH H
?
O O
(Require 2 steps)

3.
i. O3, Zn, CH3COOH
?
ii. NaBH4, MeOH, H3O+
SYNTHESIS OF
KETONES
 1. Oxidation of
o secondary
2° alcohol becomes a ketone. alcohols
o Reagents:
a. Chromic acid reagent (H2CrO4) or JONES reagent
Preparation:
- Na2Cr2O7 or K2Cr2O7 is dissolved in aqueous acid such as dilute
H2SO4
- Chromium trioxide (CrO3) is dissolved in dilute H2SO4 -JONES

b. Hot acidified KMnO4 (KMnO4/H2SO4)

c. Pyridinium chlorochromate (PCC) in CH2Cl2

d. Chromium based reagents:

i. Sarett reagent
ii. Collins reagent
 OH
O
+
R C R' KMnO4/H
R C R'
heat
H
2o alcohol ketone

OH
O
R C R' K2Cr2O7/H2SO4
R C R'
heat
H
2o alcohol ketone

OH
O
R C R' PCC
R C R'
H CH2Cl2

2o alcohol ketone

OH
O
R C R' CrO3. 2py
R C R'
H
2o alcohol ketone
 Examples:

OH
O
+
H3CH2C C CH3 KMnO4/H
H3CH2C C CH3
heat
H

OH K2Cr2O7/H2SO4
O
heat

OH O
PCC

CH2Cl2
Jones oxidation
 2. Oxidation cleavage of
alkenes
Sameby ozonolysis
as aldehydes

R R' R O R' (CH3)2S R R'

C C O3 C C C O O C
R O O H or H2O, Zn/H+
R H R H
ozonide ketone aldehyde

H+ = acetic acid

Example:

CH3
CH3
i) O3
CH3 C C CH3 O C CH3
ii) (CH3)2S CH3C O
CH3 CH3
2,3-dimethyl-2-butene propanone propanone
(ketone) (ketone)
TESTS FOR ALDEHYDES
AND KETONES

 TOLLENS’ TEST
 IODOFORM TEST
 TOLLEN’S TEST OR SILVER MIRROR TEST
FOR ALDEHYDES AND KETONES

 Test for identifying aldehydes. Simple hydrocarbons, ethers, ketones

and alcohols DO NOT REACT with Tollens’ reagent.

 Tollens’ reagent ([Ag(NH3)2]+) or called as ‘ammoniacal silver nitrate’

solution is a mixture of aqueous silver nitrate and ammonia.

 Contains the silver amine complex ion, [Ag(NH3)2]+

 Tollens’ reagent is a mild oxidising agent.

 Silver ion, Ag+ oxidized aldehyde to carboxylate ion.

 Silver ion is reduced to metallic silver in the form of a black suspension

or a silver mirror deposited on the wall of the test tube.
Complete equation:
O O
2Ag(NH3)2+ 3OH- H2O 2Ag 4NH3 2H2O
R C H R C O
aldehyde Tollens' reagent silver carboxylate

Simplified equation:
O O
R C H 2Ag+ H2O 2Ag R C OH 2H+
aldehyde Tollens' reagent silver carboxylic acid

or
O O
R C H Ag2O NH4OH EtOH 2Ag R C OH
aldehyde silver carboxylic acid

EtOH = ethanol
 Example

O O
2Ag(NH3)2+ 3OH- H2O 2Ag H3C C O 4NH3 2H2O
H3C C H
ethanal Tollens' reagent silver ethanoate

silver mirror
 IODOFORM TEST
o Iodoform test use a solution of I in an alkaline medium such as
2
NaOH or KOH (oxidising agent).

o When ethanal warmed with this solution, triiodoethanal will be

formed as the intermediate product.

o Triiodoethanal then reacts with the base to form a bright yellow

solid (triiodomethane or iodoform).

Synthetic outline or Equation:

3NaOH
CH3CHO + 3I2 CI3CHO
triidoethanal

Cl3CHO + NaOH HCOO- Na+ + CHI3 (s)

triiodomethane
(iodoform)
o Iodoform test is useful for the methyl ketone group (CH3C=O)
in ethanal and methyl ketones.
o If an alkaline solution of iodine is warmed with an organic
compound and a bright yellow solid of triiodomethane
(iodoform) is produced, the organic compound is likely to be
one of the following:

O
ethanal CH3 C H

O
a ketone with the CH3 C group
 General synthetic outline or equation for iodoform test:

O O I O
3I2 NaOH
R C CH3 R C C I R C O Na+ CHI3
3NaOH
I triiodomethane
(iodoform)
Bright yellow
solid

Example:

O O I O
3I2 NaOH
C CH3 C C I C O Na+ CHI3
3NaOH
I triiodomethane
(iodoform)
Bright yellow
solid
o Iodoform test can be used to distinguish:

i) ethanal from other aldehydes, because ethanal is the

only aldehydes that gives a positive iodoform test.

ii) methyl ketones (ketones that contain CH3CO- group) give

positive iodoform test.

For example, propanone and phenylethanone give a bright

yellow solid, but 3-pentanone and diphenylmethanone
give negative iodoform tests.
 SUMMARY OF TESTS FOR
ALDEHYDES AND KETONES

Test Reagent Observation

Tollens’ Test [Ag(NH3)2]+ Aldehyde: Formation of silver mirror.
Ketone: Silver mirror does not formed.
Iodoform I2/NaOH Positive test: Formation of bright yellow
Test solid (iodoform). Compounds which have
methyl ketone structure will give
positive test.
 Exercise
Provide the products/reagent for the following reactions. Include
intermediate(s) where necessary.

1. OH
1. H2CrO4
?
2. Zn(Hg), aq HCl

2. OH 1. NH2NH2
?
2. KOH, heat
O

3. 1. O3, Zn, CH3COOH

?
2. Ag2O, NH4OH, EtOH

4. O O
?
 Exercise
Consider the following schematic diagram

O ? O ? O
OCH3 OCH3 H
O OH OH

Compound P Hydroxyester Compound Q

1. Provide suitable reagents for the conversion of compound P to

hydroxyester and from hydroxyester to compound Q.

2. Explain why LiAlH4 could not be used in the conversion of P to Q.

 Exercise

1. Reacting ethanol with PCC gives compound X which would

also give a positive result with iodoform test.

a) Draw the structure of X and using IR spectroscopy, state how

you would confirm that X has been synthesized.
b) Explain how compound X gives a positive iodoform reaction.
You may include a synthetic outline to support your
reasoning.