You are on page 1of 87

Chapter 16:

CARBONYL COMPOUNDS
CHAPTER 16

CARBONYL
COMPOUNDS
Learning Outcomes
At the end of this lesson, students should be
able to:
Give the general formula of aldehydes and
ketones:
O O
and
R C H R C R
Draw the structures and name the carbonyl
compounds for aldehyde and ketones (parent
chain C10) for according to the IUPAC
nomenclature.
Introduction
Aldehydes and ketones contain a carbonyl
group, O
C

General formula:

O O
R C H R C R
aldehydes ketone
IUPAC Nomenclature
Aldehydes
The number of carbon atom in longest
continuous chain that contains the CHO
group provides the base name for
aldehydes.

The e ending of the corresponding alkane


name is replaced by al, and substituents
are specified in the usual way.
Example:
O
CH3CH2CH2CH2CH2 C H

hexanal

O
CH3CHCH2CH C H
CH3 CH2CH3
2-ethyl-4-methylpentanal
Example:

O
CH3CH CHCH2 C H

3-pentenal

O
CH3CHCH2 C H
OH
3-hydroxybutanal
Example:

CH2CH2CHO

3-cyclohexylpropanal

O
CHO H C C H
O
phenylmethanal
(benzaldehyde) ethanedial
IUPAC Nomenclature and Common Names
for Aldehyde Compounds
Aldehyde IUPAC
Common Name
Compound Name

HCHO methanal formaldehyde

CH3CHO ethanal acetaldehyde

CH3CH2CHO propanal propionaldehyde

CH3CH2CH2CHO butanal butyraldehyde


9
IUPAC Nomenclature
Ketones

The e ending of an alkane is replaced by


one in the longest continuous chain
containing the carbonyl group.

The chain is numbered in the direction that


provides the lower number for this group.
Example:

O
CH3CH2 C CH3
butanone @ 2-butanone @ butan-2-one

O
CH3CH2 C CH2CH2CH3

3-hexanone
Example:

O
CH3CH C CHCH3
CH3 CH3
2,4-dimethyl-3-pentanone

O
CH3CH CHCH2 C CH3
4-hexen-2-one
Example:
O
C CH2CH3

cyclohexylpropanone

H 3C
OH
O

2-hydroxy-2-methylcyclohexanone
Example:
O
C CH3

acetophenone
(phenylethanone)
O
C

Benzophenone
(diphenylketone)
IUPAC Nomenclature and Common Names
for Ketone Compounds
IUPAC Common
Ketone Compound
Name Name

CH3COCH3 propanone acetone

CH3CH2COCH3 ethyl methyl


2-butanone
ketone
n-methyl
CH3CH2CH2COCH3 2-pentanone propyl ketone

CH3CH2COCH2CH3 3-pentanone diethyl ketone


EXERCISE:

1. Write the names of the following compound


according to IUPAC nomenclature.
O CH3

H3C C C CH2
CH3

2. Write down all structural formulae of


compound with molecular formula C5H10O
and name them according to IUPAC
nomenclature.
Learning Outcomes
At the end of this lesson, students should be
able to:
Explain the preparation of carbonyl
compounds through:
i. ozonolysis of alkene
ii. Friedel-Crafts acylation to produce
aromatic ketone
iii. oxidation of alcohol
Ozonolysis of alkenes
Ozone undergoes a remarkable reaction with
alkenes in which the C=C are cleaved to give
ozonides.

Hydrolysis of the ozonides intermediate in the


presence of zinc, giving carbonyl compounds.

O
R R' i) O3 R C H
C C +
H R'' ii) Zn,H2O/H+
O
R' C R''
Example:
O
CH3 C H
ethanal
CH3CH=CHCH2CH3 i) O3 +
ii) Zn,H2O/H+
2-pentene
O
CH3CH2 C H
propanal
Example:
O
CH3CH2 C CH3
CH3 2-butanone
CH3CH2C=CHCH2CH3 i) O3 +
ii) Zn,H2O/H+
3-methyl-3-hexene
O
CH3CH2 C H
propanal
Example:

CH3 O O
i) O3
+
H C CH2CHCH2 C H
ii) Zn,H2O/H
CH3
4-methylcyclopentene 3-methylpentandial
Friedel-Crafts acylation
(aromatic ketones)

Acyl chlorides or carboxylic acid anhydride


acylate aromatic ring in the presence of
aluminium chloride.

The reaction is an electrophilic aromatic


substitution in which acylium ion generated
attack the ring.
O
O AlCl3
+ C R
R C Cl
acyl chloride aromatic ketone

Example:

O O
+ AlCl3
C CH3
CH3 C Cl

benzene acetyl chloride acetophenone


O O
+
R C O C R
benzene acid anhydride

O O
AlCl3
C R + R C OH
acid carboxylic
aromatic ketone
Oxidation of alcohols
i. Primary (1o) Alcohols

1o alcohols can be oxidised to aldehydes


by using PCC.

Example :

CH2Cl2 O
CH3CH2OH + PCC
CH3 C H
ethanol
ethanal
(1o alcohol)
(aldehyde)
ii. Secondary (2o) Alcohols

2o alcohols are oxidised to ketones by using


oxidizing agent such as PCC, chromic acid or
potassium permanganate.

Example :

OH O
H+
CH3CHCH3 + KMnO4 CH3 C CH3
2-propanol propanone
(2o alcohol) (ketone)
OH O
H+
+ K2Cr2O7

cyclopentanol cyclopentanone
(2o alcohol) (ketone)

H 3C CH3 H2Cr2O7 H3C CH3

OH O
2,5-dimethylcyclohexanol 2,5-dimethylcyclohexanone
28
Learning Outcomes
At the end of this lesson, students should be
able to:
Explain the chemical properties with
reference to:
i. nucleophilic addition with HCN, water,
alcohol, sodium bisulphate and Grignard
reagent.
ii. reduction to alcohol using LiAlH4 or
NaBH4 followed by H3O+; and H2/catalyst.
Learning Outcomes
iii. condensation with ammonia derivatives
such as hydroxylamine, hydrazine,
phenylhydrazine and 2,4 -diphenylhydrazine
(2,4-DNPH) as identification test for
carbonyl compounds.

iv. oxidation with KMnO4/H+, Cr2O72-/H+,


Tollens, Fehlings and Schiffs reagents to
diffrentiate aldehydes from ketones.

v. iodoform test to identify methyl ketone group.


1. Nucleophilic Addition
The most characteristic reaction of aldehydes
and ketones is nucleophilic addition to the
carbon-oxygen double bond.

General reaction:

Nu
R |
C = O + H - Nu R C OH
H |
H
R aldehyde or ketone
C+=O- (R or R maybe H)
R

Oxygen is more electronegative, it makes the


carbonyl carbon atom deficient in electron
tend to attack by a nucleophile.

O O- OH
| |
C -C - + H+ -C
| |
Nu: - Nu Nu
The trigonal planar arrangement of groups
around the carbonyl carbon atom makes the
carbonyl carbon atom is relatively open to be
attacked from above or below.

The positive charge on the carbonyl carbon


atom is susceptible to attack by a
nucleophile.

The negative charge on the carbonyl oxygen


atom means that nucleophilic addition is
susceptible to acid catalysis.
(a) Addition of Hydrogen Cyanide (HCN)

Hydrogen cyanide adds to aldehydes and


ketones to form cyanohydrins
(2-hydroxyalkanonitrile).

This reaction forms a product with one more


carbon atom than the reactant.

H - C N: H+ + -:C N: or CN-
O
R OH
R C H + HCN C
H CN

Cyanohydrins
O
R OH
R C R + HCN C
R CN
The HCN is prepared in situ by the reaction
of a mixture of KCN or NaCN with H2SO4.

Reagents : NaCN @ KCN (aq) followed by


dilute H2SO4.

Example:

O OH
NaCN
CH3CH2 C H CH3CH2 C H
H2SO4
CN
Example:

O OH
KCN
CH3CH2 C CH3 CH3CH2 C CH3
H2SO4
CN

O OH
NaCN
C H C H
H2SO4
CN
Cyanohydrins are useful intermediates in
organic synthesis. Acidic hydrolysis converts
cyanohydrins to -hydroxy acid .

Example:

CH3 CH3
| H + / H 2O |
CH3 C OH CH3 C OH

| |
CN COOH

cyanohydrin -hydroxy acid


(b) Addition of Water (Hydration)
Water adds to an aldehyde or to a ketone to
form a hydrate or gem-diols.
Gem-diols is a molecule with two OH group
on the same carbon .

O OH
H+
C + H 2O C
aldehyde/ketone OH
gem-diol
Example:
O OH
H+
CH3CH2 C H + H 2O CH3CH2 C H
propanal OH
propanediol

O OH
H+
CH3CH2 C CH3 + H2O CH3CH2 C CH3
butanone OH
2,2-butanediol
(c) Addition of Alcohol
(i) Hemiacetals and hemiketal
Aldehyde react with one equivalent alcohol
to form hemiacetal.

O OR
H+
R C H + ROH R C H
aldehyde
OH
hemiacetal
Ketone react with one equivalent alcohol to
form hemiketal.

O OR
H+
R C R + ROH R C R
ketone
OH
hemiketal
Example:
O OCH3
H+
CH3CH3 C H + CH3OH CH3CH2 C H
propanal OH
hemiacetal

O OCH3
H+ CH3 C CH3
CH3 C CH3 + CH3OH
propanone OH
hemiketal
(ii) Acetals and ketal
The hemiacetal reacts with a second molar
equivalent of the alcohol to produce an acetal.
An acetal has two -OR groups attached to
the same carbon atom.

OR OR
H+
R C H + ROH R C H
OH OR
hemiacetal acetal
Hemiketal undergoes similar reaction to give
ketal.

OR OR
H+
R C R + ROH R C R
OH OR
hemiketal ketal
Example:
OCH3 OCH3
H+
CH3CH2 C H + CH3OH CH3CH2 C H
OH OCH3
hemiacetal acetal

OCH3 OCH3
H+ CH3 C CH3
CH3 C CH3 + CH3OH
OH OCH3
hemiketal ketal
(d) Addition of Sodium Bisulphite (NaHSO3)

Aldehydes and ketones react with sodium


bisulphate to form bisulphate salts that are
soluble in water.

This reaction is used for purification of


aldehyde @ ketone from other non-soluble
organic compounds.

Pure carbonyl compound is obtained when


treated with aqueous base @ acid.
O OH
C + NaHSO3 C
aldehyde/ketone SO3-Na+
bisulphate salt

Example:

O OH
CH3CH2 C H + NaHSO3 CH3CH2 C H
propanal SO3-Na+
bisulphate salt
Example:

O
C CH3 + NaHSO3

OH
C CH3
SO3-Na+
bisulphate salt
(e) Addition of Grignard Reagent (RMgX)
Addition of a Grignard reagent to a carbonyl
compound, followed by hydrolysis gives a
different types of alcohol.
These Grignard reagents act as a nucleophile
which react with carbonyl compounds to yield
alcohol.

H2O/H+
R MgX + C O RCOH + Mg(OH)X
Grignard alcohol
reagent
i. Addition of a Grignard Reagent to methanal
(formaldehyde) followed by hydrolysis in
aqueous acid gives a primary alcohol.

O H
H2O/H+
R MgX + H C H RCOH + Mg(OH)X

methanal H
1o alcohol
ii. Addition of a Grignard Reagent to other
aldehyde followed by hydrolysis in aqueous
acid gives a secondary alcohol.

O R
H2O/H+
R MgX + R C H RCOH + Mg(OH)X

aldehyde H
2o alcohol
iii. Addition of a Grignard Reagent to ketone
followed by hydrolysis in aqueous acid give a
tertiary alcohol.

O R
H2O/H+
R MgX + R C R RCOH + Mg(OH)X

ketone R
3o alcohol
Example:

ether
CH3CH2Br + Mg CH3CH2MgBr

O
CH3CH2MgBr + CH3 C H

CH3
CH3CH2COH + Mg(OH)Br
H
Exercise: Past Year 2007/2008
An aldehyde, EE reacts with ethylmagnesium
bromide followed by acid hydrolysis forms
compounds FF, C6H14O. Treatment of FF with
concentrated sulphuric acid gives GG, C6H12.
Reaction of GG with ozone followed by zinc in
water yields two products, propanal and
propanone.

Identify compound EE through GG. Write an


equation for each chemical reaction involved.

Suggest another Grignard reagent and carbonyl


compound which can be used to prepare
compound FF.
2. Reduction Reactions

Aldehydes are reduced to 1o alcohols.


Ketons are reduced to 2o alcohols.

General reaction:

O [H]
R CH2OH
R C H

aldehyde 1o alcohol
General reaction:
O [H] OH
R C R R CH R

ketone 2o alcohol
The common reducing agents used are :
i. Lithium aluminium hydride (LiAlH4 in ether/
H3O+)
ii. Sodium borohydride (NaBH4 in ether/H3O+)
iii. Catalytic hydrogenation (H2 with Ni/Pt/Pd/Zn)
***[H] reducing agents
Example:

O
H2/Pt
CH3CH2CH2 C H CH3CH2CH2CH2OH
butanal butanol

O
i. LiAlH4/ether
CH3CH2CH2 C CH3
ii. H3O+ OH
2-pentanone
CH3CH2CH2 CH CH3
2-pentanol
Example:
O
i. NaBH4/ether
C H CH2OH
ii.H2O/H+

benzaldehyde phenylmethanol

O OH
i.LiAlH4/ether
ii. H3O+

cyclopentanone cyclopentanol
3. Condensation with Ammonia Derivatives
Ammonia, NH3 and its derivatives react as
nucleophile with carbonyl compounds to form
imines (compound with C=N).
Involved addition reaction followed by
dehydration (elimination of H2O molecule).
General reaction:

H3O+
C O + H 2N Z C NZ + H2O
aldehyde ammonia @ an imine
@ketone its derivatives
Z in Z-NH2 Reagent Product
H 2N H C N H
H
ammonia an imine

H 2N R C N R
R
1o amine an imine

H2N OH C N OH
OH
hydroxylamine an oxime

H2N NH2 C N NH2


NH2
hydrazine a hydrazone
Z in Z-NH2 Reagent Product

H2N NH C N NH
NH
phenylhydrazine a phenylhidrazone

O O
O
H2N NHCNH2 C N NHCNH2
NHCNH2
semicarbazide a semicarbazone
Example:
i. O H
H+
C H + NH3 C NH
ammonia + H 2O
benzaldehyde

ii.
H+ NCH3
O

+ CH3NH2
amine
+ H 2O
cyclopentanone
Example:
iii. O H
H+
CH3 C H + NH2OH CH3 C NOH
hydroxylamine + H 2O

iv.
O CH3
H+
CH3 C CH3 + N2H4 CH3 C N NH2
hydrazine + H 2O
Example:
v. O
CH3CH2 C H + H2N NH
phenylhydrazine

H+

H
CH3CH2 C N NH + H 2O
Example:
vi. O O
CH3CH2 C CH3 + H2N NHCNH2
semicarbazide

H+

CH3 O
CH3CH2 C N NHCNH2 + H 2O
Bradys Test

NH NO2
Z in Z-NH2 Function:
O2N
To identify
H2N NH NO2 the presence
of carbonyl
Reagent O2N
group (C=O)
2,4-dinitrophenylhydrazine
(2,4-DNPH)
Observation:
Formation of
C N NH NO2 orange or
Product
O2N yellow
2,4-dinitrophenylhidrazone precipitate
Example:
O
H2N NH NO2
CH3 C H +
O2N
2,4-dinitrophenylhydrazine
H+ (2,4-DNPH)

H
CH3 C N NH NO2 + H 2O
O2N

Observation: orange precipitate formed


Example:
O
H2N NH NO2
C CH3 +
O2N
2,4-dinitrophenylhydrazine
H+ (2,4-DNPH)

CH3
C N NH NO2 + H 2O
O2N

Observation: orange precipitate formed


4. Oxidation Reactions

Oxidition reaction is the basis to distinguish


aldehydes from ketones.

Aldehydes are easily oxidised to carboxylic


acids by strong oxidising agents such as
chromic acid and potassium permanganate.

Aldehydes also oxidised by mild reagents


such as Tollens reagent, Fehlings solution,
Benedicts solution and Schiffs reagent.
KMnO4 , K2Cr2O7

O O
H+
CH3(CH2)4 C H + KMnO4 CH3(CH2)4 C OH

hexanal hexanoic acid

Observation: Purple colour of solution decolourised


O O
H+
C H + K2Cr2O7 C OH

benzaldehyde benzoic acid

Observation: orange colour of solution change to


green
Tollens reagent
Tollens reagent is use to differentiate
aldehydes and ketones.

Tollens reagent is prepared by mixing aqueous


silver nitrate with aqueous ammonia.

The reagent contains the diamminosilver ion,


Ag(NH3)2+.

It oxidizes aldehydes to carboxylate anoins.


After oxidation, silver is reduced from the +1
oxidation state to metallic silver.

If the rate of reaction is slow and the walls of


the vessel are clean, metallic silver deposits on
the walls of the test tube as a mirror.

If not, it deposits as a grey or black precipitate.

Tollens reagent gives a negative result with all


ketones except -hydroxy ketones.
General equation:

O
R C H + 2[Ag(NH3)2]+ + OH-
aldehyde

2Ag + RCOO- + 2NH4+ + 2NH3


silver mirror carboxylate ion

Observation: Formation of silver mirror


known as silver-mirror test
Example:

O
CH3CH2 C H + 2[Ag(NH3)2]+ + OH-
propanal

O
CH3CH2 C O- + 2Ag + 2NH4+ + 2NH3
propanoate ion silver mirror

Observation:Formation of silver mirror


Example:
O
C H + 2[Ag(NH3)2]+ + OH-

benzaldehyde
O
C O- + 2Ag + 2NH4+ + 2NH3
silver mirror
benzoate ion

Observation:Formation of silver mirror


Fehlings reagent
Used to differentiate an aliphatic aldehyde
from aromatic aldehyde and ketone.

Fehlings solution contains Cu(II) ion, as a


complex ion in a basic solution.

It oxidises aldehydes to carboxylate ions as


the Cu2+ , which forms a brick-red precipitate,
Cu2O.

blue color of Cu2+ will fades as the red


precipitate of Cu2O forms.
General equation:

RCOH + 2Cu2+ ( tartarate ion )


5 OH-
(blue)

RCOO- + 2Cu2O + 3H2O


Copper (I) oxide
(brick red precipitate)

Observation: Formation brick red precipitate


Benedicts reagent
For Benedict test, citrate complex are used.

5OH-
RCOH + 2Cu2+ (citrate)
blue

RCOO- + Cu2O + H 2O
Copper (I) oxide
(brick red precipitate)

Observation: Formation brick red precipitate


Schiffs reagent
Schiffs reagent is use to differentiate aldehydes
and ketones.

aldehyde

positive test with Schiffs reagent


giving a pink colorisation

ketone

negative test with Schiffs reagent


Iodoform Test
(Haloform Reaction)
Iodoform test is use to identify the presence of
methyl ketone group in carbonyl compounds.

O
CH3 C
methyl ketone group

Reagent : excess I2 / NaOH


Methyl ketone is converted first into a triiodo-
substituted ketone (halogenated methyl group).
O O
3OH-
R C CH3 + 3I2 R C CI3 + 3HI + 3H2O
R = H / alkyl

Hydroxide ion attack carbonyl group to give


iodoform and carboxylate ion.

O O
R C CI3 + OH- R C O- + CHI3
Positive test gives a triiodomethane or iodoform
(CHI3) as a yellow precipitate.

Example :

O O
I2 / NaOH
CH3 C H H C O- + CHI3
methanoate ion iodoform
(yellow
precipitate)
Example :

O O
I2 / NaOH
C CH3 C O- + CHI3
benzoate ion iodoform

Observation: yellow precipitate formed


Summary of Oxidation Test
Aliphatic Aromatic Ketone
aldehyde aldehyde
Positive
Test Function O O O Observation

R C H C H R C R
Purple colour
KMnO4/H+/ X
decolourised
K2Cr2O7/H+/ Differentiate X orange to green
aldehyde from
Tollens
ketone. X Silver mirror
(Ag(NH3)2+/OH-)
Schiffs X Pink solution
Fehlings Differentiate
(Cu2+ tartarate aliphatic X X
ion/OH-) aldehyde from Brick-red
Benedict aromatic precipitate
(Cu2+ citrate aldehyde and X X
ion/OH-) ketone
To identify the
Iodoform presence of
O Yellow
(I2/OH-) methyl ketone precipitate
CH3 C
group
Exercise:

The molecular formula of an unknown compound


A is C7H14. Ozonolysis of A gave two products B
and C, whereby both B and C reacted with 2,4-
dinitrophenylhydrazine to give solid derivatives. B
gave positive results to Tollens and Iodoform
tests, while C gave negative result to both of the
tests. Suggest the structural formula of A, B and
C. Explain your answer.