CARBONYL

COMPOUNDS

1
Objective
n Describe aldehydes and ketones.
n Draw the structure and name the
compound according to IUPAC
nomenclature and common names.

2
INTRODUCTION
n Functional group: carbonyl, C=O
n General formula: CnH2nO
n Aldehyde & Ketone are isomeric
n Carbonyl compounds are polar
n In general, an aldehyde > reactive than
ketone towards nucleophilic addition
reaction

3
INTRODUCTION
n ALDEHYDE n KETONE
O δ- O δ-

C δ+ C δ+

R H R R’

n R = alkyl, aryl @ H
R & R’ = alkyl, aryl

4
Naming of Aldehyde
n Aldehyde is named by substituting the letter –
e of the corresponding alkane with –al

n Basic name depends on the longest chain with

–CHO group

n The chain must be numbered by starting with

–CHO group as C-1

5
Naming of Aldehyde
Structure IUPAC name General name
O methanal formaldehyde
H-C-H
O ethanal acetyldehyde
CH3-C-H
O propanal propionaldehyde
CH3CH2-C-H

6
Naming of Aldehyde
Structure IUPAC name General name
O butanal n-butyraldehyde
CH3CH2CH2-C-H

O pentanal n-valeraldehyde
CH3(CH2)3-C-H
O benzaldehyde benzenecarbaldehyde

Ph-C-H (phenylmethanal)

7
Naming of Aldehyde
O
O
2 1 CH2=CHCH2C-H
4 3 2 1
CH2C-H
3-butenal

H3C-H2C O
Phenylethanal
(phenylacetyldehyde) CH3CHCHC-H
4 3 2 1
OH
2-ethyl-3-hydroxybutanal

8
Naming of Ketone

n Ketone is named by substituting the letter

–e of corresponding alkane with –one

n The longest chain with carbonyl group is

numbered so that C in carbonyl group gets
the smallest number

9
Naming of Ketone
Structure IUPAC name General name
O propanone acetone
CH3CCH3 (dimethyl ketone)

O
CH3CCH2CH3 Butanone methyl ethyl ketone

O
CH3CCH2CH2CH3 2-pentanone methyl propyl ketone

10
Naming of Ketone
Structure IUPAC name General am
O acetophenone
phenylethanone (phenyl methyl ketone)
Ph-C-CH3

O benzophenone
Ph-C-Ph diphenylmethanone (diphenyl ketone)

O
CH3CH2CCH2CH3 3-pentanone diethyl ketone

11
O O
CH2C-CH3 CH2=CHCH2CCH3
5 4 3 2 1
4-penten-2-one

phenylpropanone O O
CH3CCH2CH2CCH3
1 2 3 4 5
2,5-hexanadione

O O
-CH2C-CH2- CH2CH3
1 2 3

1,3-diphenylpropanone OH

2-ethyl-2-hydroxycyclopentanone
12
EXCERCISE

1. Write the names of the following compounds according to

IUPAC nomenclature
O
CH3 O
a. c. C H 3C H 2C H 2C H C H
CH CHCH CH CH CH
3 2 2 2
CH2

CH3
O

b. C H 3C H 2C H 2C
d. CH 3CH 2C CH2CH2CH2CH3
CHCH3
O
CH3

13
2. Write down all structural formulae of compound
with molecular formula C5H10O and name them
according to IUPAC nomenclature.

14
Objective
n Explain the preparation of carbonyl compounds
through these reactions:
a)Oxidation of alcohols
b)Ozonolysis of alkenes
c) Friedel–Crafts acylation to produce aromatic
ketones

15
Preparation of Carbonyl
1. Oxidation of Alcohols
¨ [O] of 1o R-OH to form aldehyde
¨ [O] of 2o R-OH to form ketone
CH2Cl2
CH3CH2CH2CH2-OH + PCC CH3CH2CH2CH=O
1-butanol butanal

KMnO4
-OH =O
H+

cyclopentanol cyclopentanone

16
Preparation of Carbonyl
2. Ozonolysis of alkene

CH3 CH3 H
(i) O3
(i) H3CC=CHCH3 H3CC=O + O=CCH3
(ii) Zn/H2O

(i) O3
(ii) O=CH(CH2)4CH=O
(ii) Zn/H2O

17
Preparation of Carbonyl
3. Friedel-Crafts Acylation
-a good method for preparing of aromatic ketones

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

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

18
Practice Questions

(a) CH3CH(Br)CH(CH3)OH + K2Cr2O7/H2SO4

(i) O3
(b) CH3CH=CCH(CH3)2
(ii)H2O/Zn
CH3

AlCl3
(c) + -C=O
Cl
19
CHEMICAL PROPERTIES

1. Oxidation
2. Reduction
3. Nucleophilic addition reaction
4. Condensation
5. Haloform reaction

20
Objective
n 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 LiAlH4,NaBH4 and

catalytic hydrogenation.

21
1.0 Oxidation
n Aldehydes are easily oxidised to carboxylic acid by
strong oxidising reagents e.g. KMnO4/H+, K2Cr2O7/H+
n Mild oxidising agents such as Tollens’, Schiff, Fehlings’
& Benedicts’ solutions can also oxidise aldehydes.
n Ketones are resistant towards oxidation because they do
not have hydrogen attached to the carbonyl carbon
atom.

KMnO 4
RCHO + RCOOH
H
O
KMnO 4
RCR’ + No reaction
H 22
1.1 TOLLENS’ TEST
n For identifying aldehydes and ketones.
n It is a mixture of aqueous silver nitrate and
ammonia.
n It contains Ag(NH3)2+
n 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(NH 3 ) 2 ] + OH
- +
RCOO + 2 Ag + 2 NH 3 + 2 NH 4
silver
cer minmirror
per ak

Example:
Cont oh
+ -
CH 3 CH 2 CHO + 2 [Ag(NH 3 ) 2 ] + OH
- +
CH 3 CH 2 COO + 2 Ag + 2 NH 3 + 2 NH 4
cer min
silver per ak
mirror

O
+ -
CH + 2 [Ag(NH 3 ) 2 ] + OH
O
- +
C O + 2 Ag + 2 NH 3 + 2 NH 4
cer minmirror
per ak 24
silver
1.2 FEHLING and BENEDICT TEST(Cu2+
tartarate complex)

n Fehling reagent will oxidise aldehydes but

not ketones
n Used to identify aldehydes
n Reaction with aldehydes will produce
carboxylate ion and copper(I) oxide
which is red in colour.
n In this reaction copper(II) is reduced to
copper(I)
25
Equation; - -
RCHO + 4 Cu2+ + 5OH RCOO + 2Cu2O
D Brick red
blue
+ 3H2O
example
O O
- -
+
CH3CH 4 Cu2+ + 5 OH CH3CO + 2Cu2O
blue
D Brick red
+ 3H2O

26
1.3 Schiff’s reagent

n Aldehyde reacts with Schiff’s reagent

to give a pink colouration
n Ketone give negative result

27
2.0 Reduction
n 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 OH
LiAlH4
CH3CH2CH CH3CH2CH
H+
H

H2 , Ni
-C-CH3 -CH-CH3
O OH

29
Objective
n Toexplain the chemical properties
with reference to these reactions :

a) nucleophilic addition with HCN,

Grignard reagent, alcohol, sodium
bisulphite and water.

30
3.0 Nucleophilic addition
n 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.
n When carbonyl C is attacked by Nu-, breaking
the carbonyl p bond & tetrahedral
intermediate is formed
n Hybridisation of sp2 C atom changes to sp3

31
3.1 Addition of HCN
n The HCN is prepared ‘in situ’ by the reaction of a
mixture of KCN or NaCN with H2SO4

n Reagents : NaCN @ KCN (aq) followed by dilute H2SO4

H H
NaCN
-C=O -C-OH
H2SO4
CN

O OH
KCN
CH3CHCCH3 CH3-CH-C-CH3
H2SO4
CH CH CN
32
3 3
3.2 Addition of Water
n yields gem-diols

H H+ H OH
C=O + H2O C
H H OH

H3CH2C H3CH2C OH
H+ C
C=O + H2O
H3C H3C OH

33
3.3 Addition of alcohol
n Aldehyde yields hemiacetal & ketone yields hemiketal

R H+ R OH
C=O + R’OH C hemiacetal
H H OR’

R H+ R OH
C=O + R’’OH C hemiketal
R’ R’ OR’’

34
n Hemiacetal & hemiketal in acidic solution react
further to form acetal & ketal

R OH H+ R OR’’
C + R’’OH C acetal
H OR’ H OR’

R OH H+ R OR’’’
C + R’’’OH C ketal
R’ OR’’ R’ OR’’

35
Examples:-

H+ OH
C=O + CH3OH C
H H OCH3

CH3 H+ CH3 OH
C=O + CH3OH C
CH3 CH3 OCH3

36
Example:
(i)RMgX
HCHO RCH2OH 1o Alcohol
(ii)H3O+

OH
(i)RMgX
R’CHO R’-CH-R 2o Alcohol
(ii)H3O+

O OH
(i)RMgX
R’CR’’ R’-C-R’’ 3o Alcohol
(ii)H3O+
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 OH
NaHSO3 + -C-CH3 -C-CH3
OSO2-Na+

Sodium
bisulphite Bisulphite
salt

39
Objective
n To explain the chemical properties with
reference to these reactions :

a) condensation with NH3 and ammonia

derivatives eg hydrazine, phenylhydrazine,
hydroxylamine and 2,4 –
dinitrophenylhydrazine as identification
test for carbonyl compounds.

b) iodoform test to identify compounds

with these structures

40
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 O-H elimination R
addition
C=O + NH3 C C=NH + H2O
R R R
N-H
H
Carbinolamine
‘Unstable intermediate’

41
Example:
2,4-dinitrophenylhydrazine
R’ H
C=O NNH- -NO2 Brady’s
R H reagent
NO2

characteristic R’
reaction of C=NNH- -NO2 + H2O yellow @
carbonyl orange
R
compounds precipitate
NO2

42
NH3 Name Product Name
derivatives

R-NH2 @ primary C=N-R @ imine

Ar-NH2 amine
C=N-Ar

NH2NH2 hydrazine C=NNH2 Hydrazone

NH2-OH hydroxyl C=N-OH oxime

amine

43
NH3 derivatives Name Product Name

phenyl C=NNHC6H5 phenyl

NH2NHC6H5 hydrazine hydrazone
O O
semi C=NNHCNH2 semi
NH2NHCNH2 carbazide carbazone

•Carbonyl react with hydrazine @ phenylhydrazine also give

yellow precipitate

44
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:-

O OH
-C-CH3 @ -C-CH3
H

45
GENERAL REACTION:-

O O O
I2 OH-
RCCH3 RCCI3 RCO- + CHI3
OH-

OH O O O
I2 I2 OH-
RCHCH3 RCCH3 RCCI3 RCO- + CHI3
OH- OH-

46
EXAMPLE:-

O O
NaIO
CH3CH2CCH3 CH3CH2C-O- + CHI3

O O
-C-CH3 I2 / NaOH -C-O- + CHI3

47
EXAMPLE:-

O O
I2/NaOH
H-CCH3 H-C-O- + CHI3

OH O
-C-CH3 I2 / NaOH -C-O- + CHI3
H

48
Practice Questions

H+
(a) CH3CCH2CH3 + H2NNH NO2
O
NO2

H+
(b) CH3CCH2CH3 + H2NOH
O
(c) CH3CCH2CH3 + I2 / NaOH
O

(d) CH3C-CH2-Ph + LiAlH4

O
49
Practice Questions

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.

50