Vous êtes sur la page 1sur 49

CARBONYL

COMPOUND
S
1

Objective
Describe

aldehydes and ketones.


Draw the structure and name the
compound according to IUPAC
nomenclature and common names.

INTRODUCTION
Functional

group: carbonyl, C=O


General formula: CnH2nO
Aldehyde

& Ketone are isomeric


Carbonyl compounds are polar
In general, an aldehyde > reactive
than ketone towards nucleophilic
addition reaction
3

INTRODUCTION
ALDEHYDE

KETONE

O -

O -

C +

C +

= alkyl, aryl @ H

R & R = alkyl, aryl


4

Naming of Aldehyde
Aldehyde

is named by substituting the


letter e of the corresponding alkane
with al
Basic name depends on the longest
chain with CHO group
The chain must be numbered by
starting with CHO group as C-1
5

Naming of Aldehyde
Structure
O
H-C-H
O
CH3-C-H
O

IUPAC name

General
name

methanal

formaldehyde

ethanal

acetyldehyde

propanal

propionaldehyde

CH3CH2-C-H
6

Naming of Aldehyde
Structure
O

IUPAC name General name


butanal

n-butyraldehyde

pentanal

n-valeraldehyde

benzaldehyde

benzenecarbaldehyde

CH3CH2CH2-C-H
O
CH3(CH2)3-C-H
O
Ph-C-H

(phenylmethanal)

Naming of Aldehyde
O
2

CH2C-H

Phenylethanal
(phenylacetyldehyde)

CH2=CHCH2C-H
4

3-butenal

H3C-H2C O
CH3CHCHC-H
4

OH

2-ethyl-3-hydroxybutanal

Naming of Ketone
Ketone

is named by substituting the letter


e of corresponding alkane with one

The

longest chain with carbonyl group is


numbered so that C in carbonyl group gets
the smallest number

Naming of Ketone
Structure
O

IUPAC name

General name

propanone

acetone
(dimethyl ketone)

CH3CCH3
O
CH3CCH2CH3
O

Butanone

methyl ethyl ketone

CH3CCH2CH2CH3

2-pentanone

methyl propyl ketone


10

Naming of Ketone
Structure

IUPAC name

O
Ph-C-CH3

acetophenone
phenylethanone

O
Ph-C-Ph
O
CH3CH2CCH2CH3

General am
(phenyl methyl ketone)

benzophenone
diphenylmethanone

(diphenyl ketone)

3-pentanone

diethyl ketone

11

O
CH2C-CH3

CH2=CHCH2CCH3
5

2 1

4-penten-2-one

phenylpropanone

CH3CCH2CH2CCH3
1

O
-CH2C-CH21

2 3

1,3-diphenylpropanone

2 3

2,5-hexanadione

O
CH2CH3
OH
2-ethyl-2-hydroxycyclopentanone
12

EXCERCISE
1. Write the names of the following compounds according to
IUPAC nomenclature
a.

CH3

CH 3CHCH 2CH 2CH 2CH

c. C H 3C H 2C H 2C H C H
CH2
CH3

b.

C H 3C H 2C H 2C
CHCH3

d. CH 3CH 2C CH2CH2CH2CH3
O

CH3
13

2. Write down all structural formulae of compound

with molecular formula C5H10O and name them


according to IUPAC nomenclature.

14

Objective
Explain

the preparation of carbonyl


compounds through these reactions:
a)Oxidation of alcohols
b)Ozonolysis of alkenes
c) FriedelCrafts acylation to produce aromatic
ketones

15

Preparation of
Carbonyl
Oxidation of Alcohols

1.

[O] of 1o R-OH to form aldehyde


[O] of 2o R-OH to form ketone

CH3CH2CH2CH2-OH + PCC

CH2Cl2

1-butanol

CH3CH2CH2CH=O
butanal

-OH

KMnO4

=O

H+

cyclopentanol

cyclopentanone
16

Preparation of
Carbonyl
2. Ozonolysis of alkene
CH3
(i) H3CC=CHCH3

(ii)

(i) O3
(ii) Zn/H2O

(i) O3
(ii) Zn/H2O

CH3

H3CC=O + O=CCH3

O=CH(CH2)4CH=O

17

Preparation of
Carbonyl
4. Friedel-Crafts Acylation
-a good method for preparing of aromatic
ketones
O

O
+ R-C-Cl + AlCl3

+ R-C-O-C-R + AlCl3

-C-R

O
-C-R

18

Practice Questions
(a) CH3CH(Br)CH(CH3)OH + K2Cr2O7/H2SO4
(b) CH3CH=CCH(CH3)2
CH3

(c)

(i) O3
(ii)H2O/Zn

-C=O
Cl

AlCl3

19

CHEMICAL PROPERTIES
1.
2.
3.
4.
5.

Oxidation
Reduction
Nucleophilic addition reaction
Condensation
Haloform reaction
20

Objective
To

explain the chemical properties with


reference to these reactions :

a) oxidation with KMnO4, K2Cr2O7,Tollens,


Fehling, Benedict and Schiff reagents to
differentiate between aldehydes and
ketones.
b) reduction to alcohol using LiAlH 4,NaBH4
and catalytic hydrogenation.
21

1.0 Oxidation
Aldehydes are easily oxidised to carboxylic acid by
strong oxidising reagents e.g. KMnO4/H+ , K2Cr2O7/H+
Mild oxidising agents such as Tollens, Schiff, Fehlings
& Benedicts solutions can also oxidise aldehydes.
Ketones are resistant towards oxidation because they
do not have hydrogen attached to the carbonyl carbon
atom.

RCHO
O
RCR

KM nO4
H

KM nO 4
H

RCOOH

No reaction

22

1.1 TOLLENS TEST


For

identifying aldehydes and ketones.


It is a mixture of aqueous silver nitrate
and ammonia.
It contains Ag(NH3)2+
In this reaction aldehyde is oxidised to
carboxylate ion and argentum is
deposited on the wall of the the test
tube as silver mirror.
23

O
+

RCH + 2[Ag(NH3)2] + OH

RCOO + 2 Ag + 2 NH3 + 2NH4

silver mirror

CH3CH2CHO + 2[Ag(NH3)2] + OH
-

CH3CH2COO + 2 Ag + 2 NH3 + 2NH4

silver mirror

O
+

CH + 2[Ag(NH3)2] + OH

O
C O

+ 2 Ag + 2 NH3 + 2NH4
silver mirror

+
24

1.2
1.2 FEHLING
FEHLING and
and BENEDICT
BENEDICT
2+ tartarate complex)
TEST
TEST(Cu
(Cu2+
tartarate complex)
Fehling

reagent will oxidise aldehydes


but not ketones
Used to identify aldehydes
Reaction with aldehydes will produce
carboxylate ion and copper(I) oxide
which is red in colour.
In this reaction copper(II) is reduced to
copper(I)
25

Equation;
RCHO + 4 Cu2+ + 5OH
blue

RCOO + 2Cu2O

+ 3H2O

Brick red

Example
O

O
2+
CH3CH + 4 Cu + 5OH
blue

CH3CO + 2Cu2O + 3H2O

Brick red

26

1.3 Schiffs reagent


Aldehyde

reacts with Schiffs reagent


to give a pink colouration
O

RC
H

R`- NH2

OH
RC
H

- H2O

NR
`
RCH

Ketone give negative result


27

2.0
2.0 Reduction
Reduction
Reduction

Aldehydes are reduced to 1o R-OH &


ketones to 2o R-OH
Reagents (a) LiAlH4 @ NaBH4 in ether + H+
(b) Zn, H+, heat
(c) H2(g), Ni @ Pt, heat
28

Example:
O
CH3CH2CH

LiAlH4

H+

Aldehydes

-C-CH3
O

ketones

H2 , Ni

OH
CH3CH2CH

1o R-OH

-CH-CH 3
OH

2o R-OH
29

3.0 Nucleophilic addition


In

C=O, the e- density is drawn more


towards the O atom making the C atom
deficient in e. Thus, the C atom
becomes the site for Nu- attack.
When carbonyl C is attacked by Nu -,
breaking the carbonyl bond &
tetrahedral intermediate is formed
Hybridisation of sp2 C atom changes to
sp3
30

3.1 Addition of HCN


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


H
-C=O

H
NaCN
H2SO4

-C-OH
CN

O
CH3CHCCH3
CH3

KCN
H2SO4

OH
CH3-CH-C-CH3
CH3 CN

31

3.2 Addition of Water


yields

gem-diols

H+

H
C

C=O + H2O
H

H3CH2C
C=O + H2O
H 3C

OH

H+

OH

H3CH2C

OH
C

H 3C

OH

32

3.3 Addition of alcohol


Aldehyde

yields hemiacetal & ketone


yields hemiketal
R

H+

R
C

C=O + ROH
H

H+

hemiacetal
OR

OH
C

C=O + ROH
R

OH

hemiketal
OR
33

Hemiacetal

& hemiketal in acidic solution


react further to form acetal & ketal

R
H

R
R

OH
C
+ ROH

H+

OR

OR
C

OR

OH
C
+ ROH

H+

acetal
OR

OR
C

ketal
OR

34

Examples:-

OH

H+
C

C=O + CH3OH
H

CH3

H+

CH3

OH
C

C=O + CH3OH
CH3

OCH3

CH3

OCH3

35

3.3 Addition of Grignard


Reagent
Methanal react with RMgX produce 1o alcohol
Aldehydes react with RMgX produce 2o alcohol
Ketones react with RMgX produce 3o alcohol

36

Example:
HCHO

RCHO

O
RCR

(i)RMgX
(ii)H3O+

(i)RMgX
(ii)H3O+
(i)RMgX
(ii)H3O+

RCH2OH

1o Alcohol

OH
R-CH-R

2o Alcohol

OH
R-C-R

3o Alcohol

R
37

3.5 Addition of sodium


bisulphite
NaHSO3 react with aldehyde & ketone to form
carbonyl bisulphite which is 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

38

O
NaHSO3 +

-C-CH3

OH
-C-CH3
OSO2-Na+

Sodium
bisulphite

Bisulphite
salt

39

4.0 Condensation
NH3 & its derivatives react as nucleophile and
react with carbonyl compounds
Involved addition reaction followed by
dehydration (elimination of H2O molecule to
form C=N)
R
R

C=O + NH3

addition

R
C
R

O-H elimination R
N-H

C=NH +

H 2O

H
Carbinolamine
Unstable intermediate

40

Example:
2,4-dinitrophenylhydrazine
R

H
C=O

NNH-

-NO2

Bradys
reagent

NO2

characteristic
reaction of
carbonyl
compounds

R
C=NNH-

-NO2 + H2O

R
NO2

yellow @
orange
precipitate
41

NH3
derivatives

Name

R-NH2 @

primary
amine

C=N-R @

NH2NH2

hydrazin
e

C=NNH2

Hydrazone

NH2-OH

hydroxyl
amine

C=N-OH

oxime

Ar-NH2

Product

Name

imine

C=N-Ar

42

NH3
derivatives
NH2NHC6H5
O

NH2NHCNH2

Name
phenyl
hydrazin
e

Product

C=NNHC6H5
O

semi
carbazide C=NNHCNH2

Name
phenyl
hydrazone
semi
carbazone

Carbonyl react with hydrazine @ phenylhydrazine also give


yellow precipitate

43

5. Iodoform reaction
Reagent : I2 in NaOH(aq), heat forms
NaIO(Sodium iodate (i))
Formation of yellow precipitate, CHI3 ,
indicate that organic compound consist
of methyl carbonyl or methyl alcohol:OH

O
-C-CH3

-C-CH3
H

44

GENERAL REACTION:-

O
RCCH3

OH
RCHCH3

I2
OH-

I2
OH-

O
RCCH3

O
RCCI3

I2
OH-

OH

O
RCCI3

O
RCO- + CHI3

OH

O
RCO- + CHI3

45

EXAMPLE:-

O
CH3CH2CCH3

NaIO

CH3CH2C-O- + CHI3

O
-C-CH3

I2 / NaOH

-C-O-

+ CHI3

46

EXAMPLE:-

O
H-CCH3

I2/NaOH

O
H-C-O- + CHI3

OH
-C-CH3

I2 / NaOH

-C-O-

+ CHI3

47

Practice Questions
(a) CH3CCH2CH3 + H2NNH
O
(b) CH3CCH2CH3 + H2NOH

NO2

H+

NO2
H+

O
(c) CH3CCH2CH3 + I2 / NaOH
O
(d) CH3C-CH2-Ph + LiAlH4
O
48

Practice Questions
The molecular formula of an unknown compound A is C 7H14.
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.

49