Carbonyl Group

CHAPTER 2

CARBONYL GROUP
SUBTOPICS
1. Structure, reactivity and physical properties of
carbonyl compounds
2. Nomenclature of aldehydes and ketone
3. Preparation of aldehydes
- Oxidation of primary alcohols
- Reduction of acid chlorides
4. Preparation of ketones
- oxidation of secondary alcohols
- Friedel-Crafts acylation

© 2005 John Wile & Sons,Inc All rights reserved

8-2
SUBTOPICS
5. Reaction of aldehydes and ketones
- Oxidation
- Reduction
- Nucleophilic addition and mechanism
(Addition of HCN, H2O, RMgX)
-Condensation with ammonia derivatives
(hayroxylamine, hydrazine)
- Aldol condensation
- Cannizaro reaction
- Iodoform reaction
6. Laboratory test to distinguish aldehyde and
ketone 8-3
1. 0
Structure, reactivity and physical
properties of carbonyl compounds
8-4
THE CARBONYL GROUP
• In this and several following chapters, we study
the physical and chemical properties of classes
of compounds containing the carbonyl group,
C=O
• aldehydes and ketones
• carboxylic acids
• acid halides, acid anhydrides, esters, amides
8-5
• adehydes and ketones are referred as
carbonyl compounds.
• carbonyl compound has a c atom and an

o atom connected by a double bond.
• the general formula of aldehydes and

ketones is CnH2nO.
Structure
ALDEHYDE KETONE
• a carbonyl group • a carbonyl (c=o)

attached to an alkyl group are
constituent and connected to two
hydrogen alkyl groups
O O
R C H R C R'
INDUSTRIAL IMPORTANCE
• Acetone and methyl ethyl ketone are
important solvents.
• Flavorings and additives like vanilla,
cinnamon, and artificial butter.
8-8
INDUSTRIAL IMPORTANCE
O
• Formaldehyde is used in HCH
polymers like Bakelite.
Methanal
(Formal dehyde)
• Bakelite was used in electrical
insulators, radio and telephone
casings, and such diverse
products as kitchenware,
jewelry, pipe stems, and
children's toys.
© 2005 John Wile & Sons,Inc All rights reserved 8-9

PHYSICAL PROPERTIES
• 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
TABLE 1. BOILING POINTS OF SIX COMPOUNDS OF
COMPARABLE
MOLECULAR WEIGHT
Name Structural formula Molecular weight Bp (°C)

Diethyl ether CH3CH2OCH2CH3 74 34
Pentane CH3CH2CH2CH2CH3 72 36
Butanal CH3CH2CH2CHO 72 76
2-butanone CH3CH2COCH3 72 80
1-butanol CH3CH2CH2CH2OH 74 117
Propanoic acid CH3CH2COOH 74 141

TABLE 2. PHYSICAL PROPERTIES OF SELECTED ALDEHYDES AND
KETONES
IUPAC name Common name Bp (°C) Solubility

(g/100 g water)
Methanal Formaldehyde -21 Infinite
Ethanal Acetaldehyde 20 Infinite
Propanal Propionaldehyde 49 16
Butanal Butyraldehyde 76 7
Hexanal Caproaldehyde 129 Slight
Propanone Acetone 56 Infinite
2-butanone Ethyl methyl ketone 80 26
3-pentanone Diethyl ketone 101 5

2.0
Nomenclature of aldehydes and
ketone

NAMING OF ALDEHYDES
• find the largest carbon chain containing the aldehyde
functional group.
• the functional group –cho can only occur at the end

of the chain.
• carbon atom of the cho is considered as c1.
• use numbers to give the position of the aldehyde and

change the “–e” ending of an alkane to “–al”.
EXAMPLE:
O
1 2 3 4 5
H C CH2CH2CH(CH3)CH3
5 4 3 2 1
4-methyl-1-pentanal
2-methyl-5-pentanal
• OR IT CAN BE WRITTEN AS:
CH3
CH3CHCH2CH2CHO
When the -CHO functional group is
attached to a ring the suffix -
carbaldehyde is added, and the carbon
attached to that group is C1.
1
1
3
BENZALDEHYDE
• Benzaldehyde is found in
the kernels of bitter
CHO almonds
Benzaldehyde
Cinnamaldehyde
• Cinnamaldehyde is the
organic compound that
gives cinnamon its flavor
and odor.
trans-3-Phenyl-2-
propenal 8-18
a) O Cl
5-chloropentanal
b) Br
2-bromo-3,4-dimethylheptanal
AROMATIC ALDEHYDE
O
C H CHO
benzaldehyde
NAMING OF KETONES
• find the longest carbon chain containing the ketone.
• use numbers to give the position of the ketone and
change the “-e” ending of an alkane to “-anone”.
• number the chain to give C=O the smaller number
• the IUPAC retains the common names
acetone, acetophenone, and benzophenone
O O O O
Propanone Acetophenone Benzophenone 1-phenyl-1-pentanone

(Acetone)
EXAMPLE:
O
1 2 3 4 5 6 7
H3CH2C C CH2CH2CH2CH3
7 6 5 4 3 2 1
3-heptanone
5-heptanone
Exercise 1:
Write the iupac name for each compound.

Exercise 2:
Exercise 3:
Write the structural formula for the following carbonyl compounds.

a) 4-ethyl-3-methylheptanal
b) 3-hydroxy-4-methyl-5-phenylpentanal
c) 5-oxohexanal
d) 2-phenyl-3-heptanone
e) 5,6-dimethyl-6-hepten-2-one
f) 1,3-cyclohexanedione
3.0
Preparation of aldehydes
- Oxidation of primary alcohols
- Reduction of acid chlorides

PREPARATION OF ALDEHYDES:
OXIDATION OF PRIMARY ALCOHOL
O
R' OH PCC R C H
alcohol CH2Cl2 aldehyde
OH O
PCC
CH3 C H CH3 C H
CH2Cl2
ethanal
H
ethanol (primary)
PCC = Pyridinium chlorochromate

Example:
CH2OH N+ H CrO3Cl-
pyridinium chlorochromate (PCC)
cyclohexylmethanol
CHO
cyclohexanecarbaldehyde
PREPARATION OF ALDEHYDES FROM
ACYL CHLORIDE
O O
LiAlH [O-t-Bu]3
R C Cl R C H
Lithium aluminum tri(t-butoxy)hydride is a mild reducing

agent.
4.0
Preparation of ketones
- Oxidation of secondary alcohols
- Friedel-Crafts acylation

PREPARATION OF KETONES: OXIDATION OF
SECONDARY ALCOHOL
• SECONDARY ALCOHOLS ARE OXIDIZED TO KETONES.
OH O
KMnO4/H +
R' C R R' C R + H2
heat
H ketone
secondary alcohol
Example:
OH O
K2Cr2O7/H+
CH3 C CH3 CH3 C CH 3 + H2
heat
H propanone
2-propanol
PREPARATION OF KETONES:
FRIEDEL-CRAFTS ACYLATION
O
O
R C Cl
AlCl3
R
benzene
5. 0
Reaction of aldehydes and ketones
- Oxidation
- Reduction
- Nucleophilic addition and mechanism (Addition of
HCN, H2O, RMgX)
-Condensation with ammonia derivatives (hayroxylamine,
hydrazine)
- Aldol condensation
- Cannizaro reaction
- Iodoform reaction

5.1 OXIDATION OF ALDEHYDES AND
KETONES
• Aldehydes can be oxidized to carboxylic acids by a variety
of oxidizing agents such as acidified potassium
permanganate, kmno4, and potassium dichromate, K2CR2O7.
• However, ketones are difficult to oxidize.
• In oxidation of aldehydes, the hydrogen bonded to the

carbonyl carbon is replaced by the –OH group.
O O
KMnO4/H+
R C H R C OH
aldehyde heat carboxylic acid
EXAMPLE:
O
+
KMnO4/H
CH3 C H
heat
ethanal
O
CH3 C OH
ethanoic acid
5.2 REDUCTION OF ALDEHYDES AND
KETONES
• common reducing agents:
1) lithium aluminum hydride (LiALH4),
2) sodium borohydride (NaBH4) OR
3) hydrogen gas in the presence of metal catalyst
such as Ni, Pt or Pd at high temperature.
• It is the reverse process of oxidation of an alcohol.
• The reduction of a carbonyl compound occurs with

the addition of -H across the double bond to
produce –OH group.
OXIDATION AND REDUCTION OF
ALDEHYDE
OH O
oxidation
R' C H R C H
reduction
aldehyde
H
primary alcohol
red oxidation
uct
ion
O
R C OH
carboxylic acid
5.2A REDUCTION TO ALCOHOLS
• aldehydes can be reduced to 1° alcohols
• ketones can be reduced to 2° alcohols
O
R-CH reduction R-CH2 OH
An aldehyde A primary
alcohol
O OH
reduction
R-C-R' R-CH-R'
A ketone A secondary
alcohol

5.2A.1 CATALYTIC REDUCTION
• Catalytic reductions are generally carried out
from 25° to 100°C and 1 to 5 atm H2
General reaction: OH
O
Pt
H2 H2/Ni
oC, 2 atm
R' C H
R C H
25
H
aldehyde
primary alcohol
• a carbon-carbon double bond may also be reduced

under these conditions
O
2 H2
H Ni OH
trans-
© 2005 John Wile & Sons,Inc All 2-Butenal
rights reserved 1-Butanol
(Crotonaldehyde)
5.2A.2 METAL HYDRIDE REDUCTIONS
• The most common laboratory reagents for the
reduction of aldehydes and ketones are NaBH4
and LiAlH4
• both reagents are sources of hydride ion, H:-, a very
strong nucleophile
H H
Na + H-B- H Li + H- Al- H H:
H H
Sodi um Lithium aluminum Hydride ion
borohydride hydride (LAH)

NaBH4 REDUCTIONS
• the key step in metal hydride reductions is transfer of a
hydride ion to the C=O group to form a tetrahedral
from
carbonyl addition compound w ater
+
H O O BH3 Na O-H
H2 O
Na+ H-B-H + R-C-R' R-C-R' R-C-R'
H H H
from the hydride reducing agent
Example: O OH
NaBH4/H2O
H3C C H H3C C H
ethanal
H
ethanol
REDUCTION OF KETONES
General reaction:
OH
O
H2/Pt R C R'
R C R'
ketone H
secondary alcohol
EXAMPLE:
O
LiAH4/H+
H3C C CH3
propanone
OH
H3C C CH3
H
2-propanol
Reduction of Aldehyde/Ketones
5.2B Reduction To Hydrocarbons
5.2b.1 Clemensen reaction
- refluxing ketones with almagamated zinc (zinc with a layer
of Hg on the surface) in concentrated HCl reduces the
Aldehyde/ ketone to hydrocarbons.
O
Zn/Hg
R C R' R CH2 R'
ketone
conc. HCl alkane
O Zn/Hg
Examples: CH3CH2CH2CH3
CH3CH2CCH3
conc. HCl butane
butan-2-one
H
O Zn/Hg H
conc. HCl
cyclohexane
8-44
cyclohexanone
EXAMPLES:
O H
Zn/Hg
C H C H
conc. HCl H
benzaldehyde toluene
H
O Zn/Hg
C CH3
C CH3 conc. HCl H
ethylbenzene
acetophenone
5.2b Reduction to hydrocarbons
5.2B.2 Wolff-Kishner re-action
refluxing ketones with hydrazine and concentrated KOH.
O
NH2NH2
R C R' R CH2 R' N2 H2O
ketone conc. KOH alkane
Examples:
O
NH2NH2
CH3 CH2CH3
conc. KOH N2 H2O
O
CH3CH2CCHCH3 NH2NH2
CH3CH2CH2CHCH3
N2 H2O
CH3 conc. KOH 8-46
CH3
5.3 NUCLEOPHILIC ADDITION REACTION -
MECHANISM
Step 1: The nucleophile forms a bond with the electrophilic C=O carbon atom
Step 2: The alkoxide is protonated by the addition of an acid to form an alcohol.

NUCLEOPHILIC ADDITION REACTIONS
OF ALDEHYDES AND KETONES
Aldehydes more reactive toward nucleophilic addition
than ketones
• Aldehydes less sterically hindered than ketones

NUCLEOPHILIC ADDITION REACTIONS
OF ALDEHYDES AND KETONES
• Aldehydes are more reactive than ketones due to
electronic factor
• C=O of aldehyde more polarized than C=O of ketone

5.3.1 Nucleophilic Addition with
Hydrogen Cyanide (HCN)
• Aldehydes react with hydrogen cyanide

(HCN) in cold alkaline solution to produce
2-hydroxynitriles or it is known as
cyanohydrins.
NUCLEOPHILIC ADDITION OF HCN: MECHANISM
O O- H CN
[1] nucleophilic attack
R C H R C H
C N
-C N
[2] protonation
Step 1: Nucleophilic attack of –CN forms new
C-C bond.
OH
+ -CN
Step 2: Protonation of the negatively
charged O atom by HCN form the
R C H
cyanohydrin.
C N
EXAMPLE: CN- is a nucleophile which is
attracted to a positive site
of the carbonyl group.
O
CH3 C H + HCN
ethanal OH
CH3 C H
CN
2-hydroxypropanenitrile
• 2-hydroxypropanenitrile can be hydrolyzed
to give 2-hydroxypropanoic acid.
OH OH
H2O/H+
H3C C H H3C C H
reflux
CN COOH
2-hydroxypropanenitrile 2-hydroxypropanoic acid
+ NH4+
• The reaction is similar ammonium ion
with ketones.
CN is converted to COOH
5.3.2A BASE-CATALYZED ADDITION OF
WATER TO CARBONYL GROUP
• Addition of water is catalysed by both

acid and base.
• The base-catalyzed hydration nucleophile
is the hydroxide ion, which is a much
stronger nucleophile than water.
5.3.2A BASE-CATALYZED ADDITION OF
O OH
[1] nucleophilic attack
R C H R C H
-
O
HO H OH
[1] -OH attacks the carbonyl group,

cleaving the pi bond and moving an [2] protonation
electron pair onto oxygen.
OH
[2] The negative charged O atom is R C H + -OH
protonated by H2O forms the gem-diol.
OH
gem-diol
5.3.2B ACID-CATALYZED ADDITION OF
• The carbonyl group must be

protonated by acid first before a
poorer nucleophile like H2O
attacks the carbonyl group.
• The reaction involve three steps.

O [1] protonation OH OH
H OH2
R C H R C H +R C H
+ H2O
Two resonance structure
• Step 1: Protonation of the carbonyl

oxygen forms a resonance-
stabilized cation that bears a full
positive charge. 8-57
OH OH
[2] nucleophilic atack
R C H R C H
HO H H2O
H2O
[3] deprotonation
• Step 2: The nucleophile (H2O)
attacks the carbocation and
deprotonation forms the neutral
addition product in step 3. OH
• The overall result is the addition of R C H +H H2O
H and OH to the carbonyl group and
regeneration of the acid catalyst. OH
gem-diol
5.3.3 ADDITION OF GRIGNARD REAGENTS
• Addition of carbon nucleophiles is one of the most important
types of nucleophilic additions to a C=O group
• a new carbon-carbon bond is formed in the process.
• We study addition of carbon nucleophiles called

Grignard reagents
• Victor Grignard was awarded the Nobel Prize for chemistry in
1912 for their discovery and application to organic synthesis
• Grignard reagents have the general formula RMgX,
where R is an alkl or aryl group and X is a halogen

GRIGNARD REAGENTS
• Grignard reagents are prepared by adding an

alkyl or aryl halide to a suspension of Mg metal in
diethyl ether
Br eth er MgBr
+ Mg
1-Bromobutane Butylmagnesium bromide
eth er
Br + Mg MgBr
Bromobenzene Phenylmagnesium bromide

REACTIONS OF GRIGNARD REAGENT
WITH ALDEHYDES AND KETONES
TO PRODUCE ALCOHOLS
O OH
[1] R Mg-X
R C H (R') R C H (R')
[2] H2O H
aldehyde/ketone
alcohol
ADDITION OF GRIGNARD REAGENTS
TO:
O OH
i) Methanal to Produce 1° Alcohol [1] R Mg-X
H C H H C R
[2] H2O H
O OH
ii) other Aldehydes to Produce 2° Alcohol [1] R Mg-X
R C H R C H
[2] H2O
R
O OH
iii) Ketones to produce 3° Alcohol [1] R Mg-X
R C R R C R
[2] H2O
R
5.4 CONDENSATION
i) CONDENSATION WITH AMMONIA:
- condensation of ketones with ammonia will produce
imines.
- this reaction is catalyzed with acid.
O H N H
H+
R C R' H N H R C R' H2O
ketone ammonia imine
Example:
O H N H
CH3CCH2CH3 H+
H N H CH3CCH2CH3 H2O
butan-2-one ammonia
© 2005 John Wile & Sons,Inc All rights reserved butan-2-imine 8-63
II) CONDENSATION WITH HYDRAZINE:
- condensation of ketones/ aldehydes with hydrazine will
produce hydrazones.
O N NH2
H2N-NH2 H+
R C R' R C R' H 2O
ketone hydrazine
hydrazone derivative
Example:
O
H2N-NH2 H+ NNH2
H2O
hydrazine
pentan-2-one
pentan-2-one hydrazone
© 2005 John Wile & Sons, Inc

All rights reserved 8-71
EXAMPLE: Water is eliminated
O2N
H
H C O + H2N N NO2
methanal
H
2,4-dinitrophenylhydrazine
O2N
H
room temp. N NO2 + H2O
H C N
H
methanal 2,4-dinitrophenylhydrazone
EXAMPLE:
O2N
R'
R C O + H2N N NO2
ketone
H
2,4-dinitrophenylhydrazine
O2N
R'
room temp. C N N NO2 + H2O
R
H
2,4-dinitrophenylhydrazone
III) CONDENSATION WITH HYDROXYLAMINE:
• hydroxylamine reacts with ketones to form oximes.
O N OH
H2N-OH H+
R C R' R C R' H2O
ketone hydroxylamine oxime
Example:
H2N-OH H+
O N H2O
hydroxylamine
OH
phenyl-2-propanone phenyl-2-propanone oxime
8-73
IV) CONDENSATION WITH PHENYLHYDRAZINE:
- Phenylhydrazine reacts with ketones to form
phenylhydrazones.
H
H H
O
H N N N N
R C R' H+ R C R' H2O
phenylhydrazine phenylhydrazone
ketone
Example:
H H H
O H N N H+ N
H2O
N
pentan-2-one phenylhydrazine pentan-2-one phenylhydrazone
V) REACTION WITH 2,4-DINITROPHENYLHYDRAZINE (2,4-DNP):
NO2 NO2
R
R
NO2 room
C O H2N N R' C N N NO2 H2O
R' temperature
H H
ketone 2,4-dinitrophenylhydrazine 2,4-dinitrophenylhydrazone
(yellow-orange precipitate)
Example:
O NO2 NO2
CH3
NO2 room
CH3 C CH2CH3 H2N N CH3CH2 C N N NO2 H2O
temperature
H H
butan-2-one 2,4-dinitrophenylhydrazine butan-2-one 2,4-dinitrophenylhydrazone
• 2,4-Dinitrohydrazones have characteristic sharp melting points.

• The formation of a yellow or orange precipitate when 2,4-DNP reacts with an
organic compound at room temperature is used
a) As chemical test for aldehydes or ketones,
b) To identify an aldehyde or a ketone by measuring the melting point of the 8-69
2,4-
dinitrophenylhydrazone formed.
v) REACTION WITH 2,4-DINITROPHENYLHYDRAZINE (2,4-DNP):
• a solution of 2,4-DNP in methanol and

sulphuric acid is called brady’s reagent.
• Aldehydes and ketones react with 2,4-DNP
at room temperature to give a yellow-
orange precipitate of 2,4-
dinitrophenylhydrazone.
REAGENT POSITIVE TEST

ACIDITY OF α-HYDROGENS
• A carbon adjacent to a carbonyl group is called
an α-carbon, and a hydrogen bonded to it is
called an α-hydrogen α-hydrogen s
O
CH3 -C-CH2 -CH3
α-carb ons
• α-hydrogens of aldehydes, ketones, and esters are
considerably more acidic than alkane or alkene
hydrogens, but less acidic than hydroxyl hydrogens

ENOLATE ANIONS
• We account for the acidity of α-hydrogens in two
ways
• the electron-withdrawing inductive effect of the
adjacent carbonyl group weakens the C-H bond
• the negative charge on the enolate anion is delocalized
by resonance relative to the anion from an alkane or
alkene
O O O-
CH3 -C-CH2 -H + A- CH3-C-CH2 CH3 -C=CH2 + H-A
the electron-w ithdrawing res onance stabilizes the enolate anion
inductive effect of the
carbonyl weakens the C-H
bond
REACTION OF ENOLATES WITH OTHER
CARBONYL COMPOUNDS
O O O O-
C C- + C C C C
enolate second carbonyl

component
nucleophile new C-C bond
electrophile
5.5 The Aldol Reaction / Aldol condensation
O O
H3C C H H3C C H NaOH
ethanal
• in the aldol reaction, two molecules OH H O

of an aldehyde or ketone reacts H3C C C C H
with each other in the presence of H
base to form β-hydroxyl aldehyde. H
3-hydroxybutanal
• aldol = an aldehyde and an

alcohol
THE MECHANISM OF ALDOL REACTION
O O O-
H2 [1]
-
OH H C C H H2C- C H H2C C H
+ H2O
Resonance-stabilized enolate anion
• Step 1: The base removes a proton from the

α-carbon to form a resonance-stabilized
enolate anion.
H OH
O O [2] nucleophilic O- O
-
attack H2
H3C C H H2C C H H3C C C C H
H
A tetrah edal carbonyl
addition intermediate
new C-C bond
Step 2: nucleophilic addition of the enolate
anion to the carbonyl carbon of another [3]
molecule
Step 3: proton transfer from water gives the

aldol product (β-hydroxyl aldehyde) and OH O
generates another hydroxide ion H2
H3C C C C H + -OH
H
5.5.1 Dehydration of the Aldol product
• an aldol reaction is often called an aldol

condensation because the β-hydroxyl carbonyl
compound that is initially formed loses H2O by
dehydration.
• a condensation reaction is one in which a water

is eliminated during a reaction.
O -
OH H O
OH, H2O β α
2 H3C C H H3C C C C H
acetaldehyde H H
β-hydroxyl aldehyde
-
OH/-H2O
dehydration
O
H3C C C C H
H H
conjugated product
5.6 Cannizzaro reaction
• Exception to characteristic aldehyde and ketone
reactions. For carbonyl without α hydrogen
• OH¯ adds to aldehyde to give tetrahedral intermediate
• H:¯ ion is expelled as leaving group

5.6 Cannizzaro reaction
O O-
-
OH
C H C H
benzaldehyde OH
• Step 1: Addition of a –OH to the benzaldehyde.

O- O O
C H H C C O-
O H
another benzaldehyde OH
+ C H
H
• Step 2: A hydride ion transfer to the carbonyl carbon

and proton transfer to the carbonyl oxygen.
• The Cannizaro reaction is a redox reaction, therefore;

a molecule of benzaldehyde is oxidized to benzoic
acid and another is being reduced to benzyl alcohol.
5.7 Iodoform Reactions
Aldehydes and ketones having the methyl ketone (CH3CO-
group) will give a yellow/orange precipitate (positive test)
In the reaction, the hydrogen attached to the carbon
next to carbonyl carbon are substituted by halogens.
Hence, the iodoform reaction can be used to identify

the presence of the methyl carbonyl group.
• for carbonyl group, only ethanal gives a
positive iodoform test while other aldehydes
give negative test.
• methyl ketones give a positive iodoform test.
• both aldehydes and ketones contain of the
carbonyl group, however the presence of
the hydrogen on the carbonyl group gives
aldehyde the reducing properties.
• therefore, aldehydes are easily oxidized

by strong oxidizing agents.
TOLLENS’ TEST
• tollens’ reagent is a colorless reagent.
• when tollens’ reagent is added to an
aldehyde, the complexes silver ion is reduced
to silver metal to form grey precipitation.
• The appearance of silver mirror on the
inner wall of the test tube is a positive test
for the aldehydes.
FEHLING’S AND BENEDICT’S TESTS
• Fehling and benedict solution contain

Cu2+ ions in an alkaline medium.
• On warming, aldehydes reduce the blue
color of Fehling/Benedict’s solution to
brick-red precipitate.
• ketones do not react with tollens’ and
fehling or benedict reagents because they
do not have the hydrogen atom in the
structure that attach to the carbon atom.
O
R C R'
TESTS TO DISTINGUISH ALDEHYDES AND KETONES AND
ALIPHATIC ALDEHYDES AND AROMATIC ALDEHYDES
TESTS ALDEHYDES KETONES
Tollens’ Test / silver mirror test Observation: Observation:

Reagent and condition: Formation of silver mirror Silver mirror did not formed
- ammoniacal silver nitrate * Ketones do not react with
solution ([Ag(NH3)2]+) Tollens’ reagent
Fehling’s test / Benedict’s test Observation; Observation:
Reagent and condition: Blue colour of the Blue colour remains.
-Solution of Cu2+ (aq) ions in Fehling’s solution * Ketones do not react with
an alkaline solution of sodium dissappears and brick-red Fehling’s/Benedict’s reagent
potassium tartate. precipitate is obtained
* Except benzaldehyde
*Can be used to distinguish
between:
i) Aldehydes and ketones
ii) Aliphatic aldehydes and
benzaldehyde
Schiff’s test Observation: Ketones (except propanone)
Reagent and condition: Formation of magenta- do not react with Schiff’s
- Schiff’s reagent pink colour (simple reagent.
aldehydes)
* Except benzaldehyde
© 2005 John Wile & Sons,Inc and a few aromatic 8-93
All rights reserved
aldehydes)
TESTS TO DISTINGUISH CARBONYL COMPOUNDS FROM
NON-CARBONYL COMPOUNDS
TESTS CARBONYL COMPOUNDS NON-CARBONYL

(ALDEHYDES AND COMPOUNDS
KETONES)
Brady’s test Observation: Observation:
Reagent: Formation of orange Orange precipitate did
- A solution of 2,4-DNP precipitate not formed
in methanol and
sulfuric acid
Condition:
Room temperature

Carbonyl Group

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CHAPTER 2

© 2005 John Wile & Sons,Inc All rights reserved

© 2005 John Wile & Sons,Inc All rights reserved

© 2005 John Wile & Sons,Inc All rights reserved

• carbonyl compound has a c atom and an

• the general formula of aldehydes and

• a carbonyl group • a carbonyl (c=o)

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• aldehydes and ketones are polar compounds and

Name Structural formula Molecular weight Bp (°C)

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IUPAC name Common name Bp (°C) Solubility

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• the functional group –cho can only occur at the end

• carbon atom of the cho is considered as c1.

• use numbers to give the position of the aldehyde and

Propanone Acetophenone Benzophenone 1-phenyl-1-pentanone

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Write the structural formula for the following carbonyl compounds.

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PCC = Pyridinium chlorochromate

Lithium aluminum tri(t-butoxy)hydride is a mild reducing

- Oxidation of secondary alcohols

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• In oxidation of aldehydes, the hydrogen bonded to the

• The reduction of a carbonyl compound occurs with

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• a carbon-carbon double bond may also be reduced

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Step 2: The alkoxide is protonated by the addition of an acid to form an alcohol.

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• Aldehydes react with hydrogen cyanide

• Addition of water is catalysed by both

[1] -OH attacks the carbonyl group,

• The carbonyl group must be

• The reaction involve three steps.

• Step 1: Protonation of the carbonyl

• We study addition of carbon nucleophiles called

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• Grignard reagents are prepared by adding an

Bromobenzene Phenylmagnesium bromide

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© 2005 John Wile & Sons, Inc

© 2005 John Wile & Sons,Inc All rights reserved

• 2,4-Dinitrohydrazones have characteristic sharp melting points.

• a solution of 2,4-DNP in methanol and

REAGENT POSITIVE TEST

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enolate second carbonyl

• in the aldol reaction, two molecules OH H O

• aldol = an aldehyde and an

• Step 1: The base removes a proton from the

Step 3: proton transfer from water gives the

• an aldol reaction is often called an aldol

• a condensation reaction is one in which a water