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COMPOUNDS
1
Objective
Describe aldehydes and ketones.
Draw the structure and name the
compound according to IUPAC
nomenclature and common names.
2
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 δ- O δ-
C δ+ C δ+
R H R R’
R = 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 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
9
Naming of Ketone
Structure IUPAC name General name
O propanone acetone
CH3CCH3 (dimethyl ketone)
O
CH3CCH2CH3 Butanone methyl ethyl ketone
O3CCH2CH2CH3
CH
2-pentanone methyl propyl ketone
10
Naming of Ketone
Structure IUPAC name General am
O acetophenone
Ph-C-CH3 phenylethanone (phenyl methyl ketone)
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
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 C5H10 O 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) 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
4. 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
(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
To explain the chemical properties with
reference to these reactions :
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.
KMnO 4
RCHO + RCOOH
H
O
KMnO 4
RCR’ + No reaction
H 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 + 2Ag + 2 NH3 + 2NH4
cerminmirror
silver perak
Contoh
Example:
+ -
CH3CH2CHO + 2[Ag(NH3)2] + OH
- +
CH3CH2COO + 2 Ag + 2 NH3 + 2NH4
cermin
silver perak
mirror
O
+ -
CH + 2[Ag(NH3)2] + OH
O
- +
C O + 2 Ag + 2 NH3 + 2NH4
cerminmirror
silver perak 24
1.2 FEHLING and BENEDICT TEST(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 RCOO + 2Cu2O
∆ Brick red
blue
+ 3H2O
example
O O
- -
+ 2+
CH3CH 4 Cu + 5OH CH3CO + 2Cu2O
blue
∆ Brick red
+ 3H2O
26
1.3 Schiff’s reagent
Aldehyde reacts with Schiff’s reagent to
give a pink colouration
Ketone give negative result
27
2.0 Reduction
Reduction
Aldehydes are reduced to 1o R-OH & ketones to 2o R-
OH
28
Example:
O OH
LiAlH4
CH3CH2CH CH3CH2CH
H+
H
H2 , Ni
-C-CH3 -CH-CH3
O OH
29
Objective
Toexplain the chemical properties
with reference to these reactions :
30
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 π bond & tetrahedral intermediate
is formed
Hybridisation of sp2 C atom changes to sp3
31
3.1 Addition of HCN
The HCN is prepared ‘in situ’ by the reaction of a
mixture of KCN or NaCN with H2SO4
H H
NaCN
-C=O -C-OH
H2SO4
CN
O OH
KCN
CH3CHCCH3 CH3-CH-C-CH3
H2SO4
CH3 CH3 CN
32
3.2 Addition of Water
yields gem-diols
H H+ H OH
C=O + H2O C
H H OH
H3CH2C H3CH2C OH
H+ C
C=O + H2O
H 3C H 3C OH
33
3.3 Addition of alcohol
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
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
To explain the chemical properties with
reference to these reactions :
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 R orange
compounds precipitate
NO2
42
NH3 derivatives Name Product Name
43
NH3 derivatives Name Product Name
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
50